Abstract
Mass production of highly efficient, durable, and inexpensive single atomic catalysts is currently the major challenge associated with the oxygen reduction reaction (ORR) for fuel cells. In this study, we develop a general strategy that uses a simple ultrasonic atomization coupling with pyrolysis and calcination process to synthesize single atomic FeNC catalysts (FeNC SACs) at large scale. The microstructure characterizations confirm that the active centers root in the single atomic Fe sites chelating to the four-fold pyridinic N atoms. The identified specific Fe active sites with the variable valence states facilitate the transfer of electrons, endowing the FeNC SACs with excellent electrochemical ORR activity. The FeNC SACs were used as cathode catalysts in a homemade Zn-air battery, giving an open-circuit voltage (OCV) of 1.43 V, which is substantially higher than that of commercial Pt/C catalysts. This study provides a simple approach to the synthesis of single atomic catalysts at large scale.
摘要
燃料电池中氧还原反应(ORR)目前面临的主要挑战是如何 大规模生产高效、耐用、廉价的单原子催化剂. 针对这个问题, 我 们开发了一种通用的策略, 即利用简单的超声雾化耦合热解和煅 烧过程来大规模合成单原子FeNC催化剂(FeNC SACs). 通过微观 结构表征发现, 活性中心位于与四吡啶N原子螯合的单原子Fe位 点. 具有特定可识别的、不同价态的Fe活性位点促进了电子的转 移, 使FeNC SACs具有良好的电化学ORR活性. FeNC SACs被用作 自制的锌空气电池阴极催化剂时, 其开路电压为1.43 V, 远高于商 业Pt/C催化剂. 本研究为大规模合成单原子催化剂提供了一种简单 有效的方法.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Stamenkovic VR, Strmcnik D, Lopes PP, et al. Energy and fuels from electrochemical interfaces. Nat Mater, 2016, 16: 57–69
Chu S, Cui Y, Liu N. The path towards sustainable energy. Nat Mater, 2016, 16: 16–22
Chen Y, Ji S, Zhao S, et al. Enhanced oxygen reduction with single-atomic-site iron catalysts for a zinc-air battery and hydrogen-air fuel cell. Nat Commun, 2018, 9: 5422
Tiwari JN, Tiwari RN, Singh G, et al. Recent progress in the development of anode and cathode catalysts for direct methanol fuel cells. Nano Energy, 2013, 2: 553–578
Shao M, Chang Q, Dodelet JP, et al. Recent advances in electro-catalysts for oxygen reduction reaction. Chem Rev, 2016, 116: 3594–3657
Mori K, Sano T, Kobayashi H, et al. Surface engineering of a supported PdAg catalyst for hydrogenation of CO2 to formic acid: Elucidating the active Pd atoms in alloy nanoparticles. J Am Chem Soc, 2018, 140: 8902–8909
Yan Z, He G, Shen PK, et al. MoC-graphite composite as a Pt electrocatalyst support for highly active methanol oxidation and oxygen reduction reaction. J Mater Chem A, 2014, 2: 4014
Nie Y, Li L, Wei Z. Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction. Chem Soc Rev, 2015, 44: 2168–2201
Ma J, Tong X, Wang J, et al. Rare-earth metal oxide hybridized PtFe nanocrystals synthesized via microfluidic process for enhanced electrochemical catalytic performance. Electrochim Acta, 2019, 299: 80–88
Xu Q, Guo CX, Tian S, et al. Coordination structure dominated performance of single-atomic Pt catalyst for anti-Markovnikov hydroboration of alkenes. Sci China Mater, 2020, 63: 972–981
Garçon M, Bakewell C, Sackman GA, et al. A hexagonal planar transition-metal complex. Nature, 2019, 574: 390–393
Song Y, Hart KT, Dooley KM. Waste-reducing catalytic oxidation of m-xylene to m-toluic acid. Catal Lett, 2016, 146: 1213–1220
Song Y, Hart KT, Dooley KM. Waste-reducing catalysis for acy-lation of a secondary amine: Synthesis ofdeet. Catal Lett, 2004, 98: 69–75
Jasinski R. A new fuel cell cathode catalyst. Nature, 1964, 201: 1212–1213
Huang K, Zhang L, Xu T, et al. −60 °C solution synthesis of atomically dispersed cobalt electrocatalyst with superior performance. Nat Commun, 2019, 10: 606
Liu X, Wang L, Yu P, et al. A stable bifunctional catalyst for rechargeable zinc-air batteries: Iron-cobalt nanoparticles embedded in a nitrogen-doped 3D carbon matrix. Angew Chem Int Ed, 2018, 57: 16166–16170
Huang X, Zhang Y, Shen H, et al. N-doped carbon nanosheet networks with favorable active sites triggered by metal nano-particles as bifunctional oxygen electrocatalysts. ACS Energy Lett, 2018, 3: 2914–2920
Sun T, Tian B, Lu J, et al. Recent advances in Fe (or Co)/N/C electrocatalysts for the oxygen reduction reaction in polymer electrolyte membrane fuel cells. J Mater Chem A, 2017, 5: 18933–18950
Wang D, Astruc D. The recent development of efficient earth-abundant transition-metal nanocatalysts. Chem Soc Rev, 2017, 46: 816–854
Leonard ND, Wagner S, Luo F, et al. Deconvolution of utilization, site density, and turnover frequency of Fe-nitrogen-carbon oxygen reduction reaction catalysts prepared with secondary N-precursors. ACS Catal, 2018, 8: 1640–1647
Ren J, Antonietti M, Fellinger TP. Efficient water splitting using a simple Ni/N/C paper electrocatalyst. Adv Energy Mater, 2015, 5: 1401660
Jiang WJ, Gu L, Li L, et al. Understanding the high activity of Fe-N-C electrocatalysts in oxygen reduction: Fe/Fe3C nanoparticles boost the activity of Fe-Nx. J Am Chem Soc, 2016, 138: 3570–3578
Kim SJ, Mahmood J, Kim C, et al. Defect-free encapsulation of Fe0 in 2D fused organic networks as a durable oxygen reduction electrocatalyst. J Am Chem Soc, 2018, 140: 1737–1742
Kramm UI, Herrmann-Geppert I, Behrends J, et al. On an easy way to prepare metal-nitrogen doped carbon with exclusive presence of MeN4-type sites active for the ORR. J Am Chem Soc, 2016, 138: 635–640
Xu H, Cheng D, Cao D, et al. A universal principle for a rational design of single-atom electrocatalysts. Nat Catal, 2018, 1: 339–348
Pan Y, Lin R, Chen Y, et al. Design of single-atom Co-N5 catalytic site: A robust electrocatalyst for CO2 reduction with nearly 100% CO selectivity and remarkable stability. J Am Chem Soc, 2018, 140: 4218–4221
Yang Z, Chen B, Chen W, et al. Directly transforming copper (I) oxide bulk into isolated single-atom copper sites catalyst through gas-transport approach. Nat Commun, 2019, 10: 3734
He X, He Q, Deng Y, et al. A versatile route to fabricate single atom catalysts with high chemoselectivity and regioselectivity in hydrogenation. Nat Commun, 2019, 10: 3663
Chen Y, Li Z, Zhu Y, et al. Atomic Fe dispersed on N-doped carbon hollow nanospheres for high-efficiency electrocatalytic oxygen reduction. Adv Mater, 2019, 31: 1806312
Liu P, Zhao Y, Qin R, et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science, 2016, 352: 797–800
Han X, Ling X, Wang Y, et al. Generation of nanoparticle, atomic-cluster, and single-atom cobalt catalysts from zeolitic imidazole frameworks by spatial isolation and their use in zinc-air batteries. Angew Chem Int Ed, 2019, 58: 5359–5364
Tian X, Lu XF, Xia BY, et al. Advanced electrocatalysts for the oxygen reduction reaction in energy conversion technologies. Joule, 2020, 4: 45–68
Ruggeri S, Dodelet JP. Influence of structural properties of pristine carbon blacks on activity of Fe/N/C cathode catalysts for PEFCs. J Electrochem Soc, 2007, 154: B761
Zhang Z, Sun J, Wang F, et al. Efficient oxygen reduction reaction (ORR) catalysts based on single iron atoms dispersed on a hierarchically structured porous carbon framework. Angew Chem Int Ed, 2018, 57: 9038–9043
Lin Y, Liu P, Velasco E, et al. Fabricating single-atom catalysts from chelating metal in open frameworks. Adv Mater, 2019, 31: 1808193
Cao R, Thapa R, Kim H, et al. Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst. Nat Commun, 2013, 4: 2076
Wang H, Maiyalagan T, Wang X. Review on recent progress in nitrogen-doped graphene: Synthesis, characterization, and its potential applications. ACS Catal, 2012, 2: 781–794
Mun Y, Kim MJ, Park SA, et al. Soft-template synthesis of meso-porous non-precious metal catalyst with Fe-N-X/C active sites for oxygen reduction reaction in fuel cells. Appl Catal B-Environ, 2018, 222: 191–199
Mun Y, Lee S, Kim K, et al. Versatile strategy for tuning ORR activity of a single Fe-N4 site by controlling electron-withdrawing/donating properties of a carbon plane. J Am Chem Soc, 2019, 141: 6254–6262
Wang J, Wang Z, Li S, et al. Surface and interface engineering of FePt/C nanocatalysts for electro-catalytic methanol oxidation: Enhanced activity and durability. Nanoscale, 2017, 9: 4066–4075
Cao L, Liu W, Luo Q, et al. Atomically dispersed iron hydroxide anchored on Pt for preferential oxidation of CO in H2. Nature, 2019, 565: 631–635
Zitolo A, Goellner V, Armel V, et al. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat Mater, 2015, 14: 937–942
Wan X, Liu X, Li Y, et al. Fe-N-C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells. Nat Catal, 2019, 2: 259–268
Lai Q, Zheng L, Liang Y, et al. Metal-organic-framework-derived Fe-N/C electrocatalyst with five-coordinated Fe-Nx sites for advanced oxygen reduction in acid media. ACS Catal, 2017, 7: 1655–1663
Kramm UI, Herranz J, Larouche N, et al. Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in pem fuel cells. Phys Chem Chem Phys, 2012, 14: 11673–11688
Jia Q, Ramaswamy N, Tylus U, et al. Spectroscopic insights into the nature of active sites in iron-nitrogen-carbon electrocatalysts for oxygen reduction in acid. Nano Energy, 2016, 29: 65–82
Walker FA, Simonis U. Iron porphyrin chemistry. Secondary Iron Porphyrin Chemistry. San Francisco: John Wiley & Sons, Ltd., 2006
Crabtree RH. The Organometallic Chemistry of the Transition Metals. 4th ed. Chichester: John Wiley & Sons, Inc., 2005
Sa YJ, Seo DJ, Woo J, et al. A general approach to preferential formation of active Fe-Nx sites in Fe–N/C electrocatalysts for efficient oxygen reduction reaction. J Am Chem Soc, 2016, 138: 15046–15056
Sougrati MT, Goellner V, Schuppert AK, et al. Probing active sites in iron-based catalysts for oxygen electro-reduction: A temperature-dependent 57Fe Mössbauer spectroscopy study. Catal Today, 2016, 262: 110–120
Masa J, Batchelor-McAuley C, Schuhmann W, et al. Koutecky-Levich analysis applied to nanoparticle modified rotating disk electrodes: Electrocatalysis or misinterpretation. Nano Res, 2013, 7: 71–78
Zhou R, Zheng Y, Jaroniec M, et al. Determination of the electron transfer number for the oxygen reduction reaction: From theory to experiment. ACS Catal, 2016, 6: 4720–4728
Guo D, Shibuya R, Akiba C, et al. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science, 2016, 351: 361–365
Lai L, Potts JR, Zhan D, et al. Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy Environ Sci, 2012, 5: 7936
Acknowledgements
This work was supported by the National Natural Science Foundation of China (NSFC, 51971029), the NSFC-BRICS STI Framework Program (51861145309), the National S&T Major Project (2018ZX10301201), the Joint Research Project of University of Science and Technology Beijing & Taipei University of Technology (TW2018007), the “1125” Zhihui Zhengzhou Talent Project of Henan Province (39080070), the Fundamental Research Funds for the Central Universities (FRF-BR-15-027A). Yujun Song also appreciates the fund supports from the “100 talent plan” fund of Fujian province (Contract No: 2017-802). This research used 9-BM beamline at the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Yujun Song appreciates Dr. Zhang from ZKKF (Beijing) Science & Technology Co., Ltd., for the HAADF-STEM characterization.
Author information
Authors and Affiliations
Contributions
Song Y designed the project, engineered the SAC samples, and discussed with Deng Y. Song Y and Wu T designed the experiment of the XAS characterization of SACs. Ma J performed the catalyst preparation and the characterization of the related microstructure and catalytic performance. Wu T and Wang L conducted the EXAFS and XANES experiments. Ma J and Wang L wrote the paper, revised by Song Y, Deng Y and Zhang W. All authors took part in the data analysis.
Corresponding authors
Additional information
Conflict of interest
The authors declare that they have no conflict of interest.
Supplementary information
Experimental details and supporting data are available in the online version of the paper
Jugang Ma is currently a PhD student at the University of Science and Technology Beijing (USTB) under the direction of Prof. Yujun Song. His main research interests are focused on electrocatalyst synthesis and the related application in fuel cells.
Yujun Song has been a full Professor in physics and applied physics at the USTB, Deputy director of the Center for Modern Physics Research since 2014. His research interests are currently focused on micro/nano-material-mediated integration innovation of modern physics with biomedical engineering, new energy and catalysis, and information science and technology.
Electronic Supplementary Material
40843_2020_1464_MOESM1_ESM.pdf
Mass production of high-performance single atomic FeNC electrocatalysts via sequenced ultrasonic atomization and pyrolysis process
Rights and permissions
About this article
Cite this article
Ma, J., Wang, L., Deng, Y. et al. Mass production of high-performance single atomic FeNC electrocatalysts via sequenced ultrasonic atomization and pyrolysis process. Sci. China Mater. 64, 631–641 (2021). https://doi.org/10.1007/s40843-020-1464-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-020-1464-6