Phthalocyanine Precursors To Construct Atomically Dispersed Iron Electrocatalysts

Wang, Yang; Wang, Maoyu; Zhang, Zisheng; Wang, Qi; Jiang, Zhan; Lucero, Marcos; Zhang, Xing; Li, Xiaoxiao; Gu, Meng; Feng, Zhenxing; Liang, Yongye

doi:10.1021/acscatal.9b01617

Phthalocyanine Precursors To Construct Atomically Dispersed Iron Electrocatalysts

Journal Article · Wed Jun 05 00:00:00 EDT 2019 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.9b01617· OSTI ID:1545882

Wang, Yang ^[1]; Wang, Maoyu ^[2]; Zhang, Zisheng ^[3]; Wang, Qi ^[3]; Jiang, Zhan ^[1]; Lucero, Marcos ^[2]; Zhang, Xing ^[3]; Li, Xiaoxiao ^[3]; ^[3]; ^[2]; ^[3]

Southern Univ. of Science and Technology, Shenzhen (China); Harbin Inst. of Technology, Harbin (China)
Oregon State Univ., Corvallis, OR (United States)
Southern Univ. of Science and Technology, Shenzhen (China)

Carbon materials embedded with atomically dispersed metal sites have recently demonstrated intriguing performance as electrocatalysts. However, it remains challenging to construct abundant single metal atoms due to easy aggregation of metal species during the high-temperature synthesis. In this work, a facile method is developed to construct single iron atom electrocatalysts with high iron content by employing iron phthalocyanine (FePc) derivatives as metal precursors. FePc molecules are encapsulated into the zeolitic imidazolate frameworks (ZIFs), and the subsequent pyrolysis yields the catalysts. Cyano substitution on FePc (FePc(CN)₈) can facilitate introduction of phthalocyanine molecules and formation of active sites, thus affording higher activity for the oxygen reduction reaction than the FePc counterpart. It is also found that adding iron salt with FePc(CN)₈ can afford a better catalyst with enhanced surface Fe–N_x content, which exhibits high activities with a half-wave potential of 0.910 and 0.811 V versus reversible hydrogen electrode in alkaline and acidic conditions, respectively. Moreover, FePc(CN)₈/ZIF-derived catalyst exhibits high selectivities and good activities for carbon monoxide production in the carbon dioxide reduction reaction (CO₂RR). The bulk Fe–N_x sites are found to be more stable than the surface Fe–N_x sites possibly due to the improved desorption of carbon monoxide.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); National Science Foundation (NSF); Shenzhen Fundamental Research Funding; USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1545882

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 7 Vol. 9; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

References (52)

Hybrid of Iron Nitride and Nitrogen-Doped Graphene Aerogel as Synergistic Catalyst for Oxygen Reduction Reaction Yin, Han; Zhang, Chenzhen; Liu, Fei Advanced Functional Materials, Vol. 24, Issue 20 https://doi.org/10.1002/adfm.201303902	journal	February 2014
Iron-Nitrogen-Doped Vertically Aligned Carbon Nanotube Electrocatalyst for the Oxygen Reduction Reaction Yasuda, Satoshi; Furuya, Atom; Uchibori, Yosuke Advanced Functional Materials, Vol. 26, Issue 5 https://doi.org/10.1002/adfm.201503613	journal	December 2015
High-Performance Electrocatalysts for Oxygen Reduction Derived from Cobalt Porphyrin-Based Conjugated Mesoporous Polymers Wu, Zhong-Shuai; Chen, Long; Liu, Junzhi Advanced Materials, Vol. 26, Issue 9 https://doi.org/10.1002/adma.201304147	journal	November 2013
Meso/Macroporous Nitrogen-Doped Carbon Architectures with Iron Carbide Encapsulated in Graphitic Layers as an Efficient and Robust Catalyst for the Oxygen Reduction Reaction in Both Acidic and Alkaline Solutions Xiao, Meiling; Zhu, Jianbing; Feng, Ligang Advanced Materials, Vol. 27, Issue 15 https://doi.org/10.1002/adma.201500262	journal	March 2015
Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis Wan, Gang; Yang, Ce; Zhao, Wanpeng Advanced Materials, Vol. 29, Issue 47 https://doi.org/10.1002/adma.201703436	journal	November 2017
Tuning the Activity of Carbon for Electrocatalytic Hydrogen Evolution via an Iridium-Cobalt Alloy Core Encapsulated in Nitrogen-Doped Carbon Cages Jiang, Peng; Chen, Jitang; Wang, Changlai Advanced Materials, Vol. 30, Issue 9 https://doi.org/10.1002/adma.201705324	journal	January 2018
Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin Advanced Materials, Vol. 30, Issue 11 https://doi.org/10.1002/adma.201706758	journal	January 2018
O-, N-Atoms-Coordinated Mn Cofactors within a Graphene Framework as Bioinspired Oxygen Reduction Reaction Electrocatalysts Yang, Yang; Mao, Kaitian; Gao, Shiqi Advanced Materials, Vol. 30, Issue 28 https://doi.org/10.1002/adma.201801732	journal	May 2018
Post Iron Decoration of Mesoporous Nitrogen-Doped Carbon Spheres for Efficient Electrochemical Oxygen Reduction Liu, Zhuang; Sun, Fei; Gu, Lin Advanced Energy Materials, Vol. 7, Issue 22 https://doi.org/10.1002/aenm.201701154	journal	August 2017
Electrochemical CO ₂ Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene Zhang, Chenhao; Yang, Shize; Wu, Jingjie Advanced Energy Materials, Vol. 8, Issue 19 https://doi.org/10.1002/aenm.201703487	journal	March 2018
A Porphyrin/Graphene Framework: A Highly Efficient and Robust Electrocatalyst for Carbon Dioxide Reduction Choi, Jaecheol; Wagner, Pawel; Jalili, Rouhollah Advanced Energy Materials, Vol. 8, Issue 26 https://doi.org/10.1002/aenm.201801280	journal	July 2018
Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts Hu, Yang; Jensen, Jens Oluf; Zhang, Wei Angewandte Chemie International Edition, Vol. 53, Issue 14 https://doi.org/10.1002/anie.201400358	journal	February 2014
Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO ₂ Electroreduction to CO and Hydrocarbons Varela, Ana Sofia; Ranjbar Sahraie, Nastaran; Steinberg, Julian Angewandte Chemie International Edition, Vol. 54, Issue 37 https://doi.org/10.1002/anie.201502099	journal	July 2015
Reactivity Descriptors for the Activity of Molecular MN4 Catalysts for the Oxygen Reduction Reaction Zagal, José H.; Koper, Marc T. M. Angewandte Chemie International Edition, Vol. 55, Issue 47 https://doi.org/10.1002/anie.201604311	journal	September 2016
Isolated Single Iron Atoms Anchored on N-Doped Porous Carbon as an Efficient Electrocatalyst for the Oxygen Reduction Reaction Chen, Yuanjun; Ji, Shufang; Wang, Yanggang Angewandte Chemie International Edition, Vol. 56, Issue 24 https://doi.org/10.1002/anie.201702473	journal	April 2017
From Metal-Organic Frameworks to Single-Atom Fe Implanted N-doped Porous Carbons: Efficient Oxygen Reduction in Both Alkaline and Acidic Media Jiao, Long; Wan, Gang; Zhang, Rui Angewandte Chemie International Edition, Vol. 57, Issue 28 https://doi.org/10.1002/anie.201803262	journal	June 2018
Controlling the Self-Metalation Rate of Tetraphenylporphyrins on Cu(111) via Cyano Functionalization Lepper, Michael; Köbl, Julia; Zhang, Liang Angewandte Chemie International Edition, Vol. 57, Issue 32 https://doi.org/10.1002/anie.201803601	journal	June 2018
Efficient Oxygen Reduction Reaction (ORR) Catalysts Based on Single Iron Atoms Dispersed on a Hierarchically Structured Porous Carbon Framework Zhang, Zhengping; Sun, Junting; Wang, Feng Angewandte Chemie International Edition, Vol. 57, Issue 29 https://doi.org/10.1002/anie.201804958	journal	June 2018
Directly converting Fe-doped metal–organic frameworks into highly active and stable Fe-N-C catalysts for oxygen reduction in acid Wang, Xiaojuan; Zhang, Hanguang; Lin, Honghong Nano Energy, Vol. 25 https://doi.org/10.1016/j.nanoen.2016.04.042	journal	July 2016
Surface functionalization of ZIF-8 with ammonium ferric citrate toward high exposure of Fe-N active sites for efficient oxygen and carbon dioxide electroreduction Ye, Yifan; Cai, Fan; Li, Haobo Nano Energy, Vol. 38 https://doi.org/10.1016/j.nanoen.2017.05.042	journal	August 2017
Recent Advances in Electrocatalysts for Oxygen Reduction Reaction Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol Chemical Reviews, Vol. 116, Issue 6 https://doi.org/10.1021/acs.chemrev.5b00462	journal	February 2016
Metal–Organic-Framework-Derived Fe-N/C Electrocatalyst with Five-Coordinated Fe-N _x Sites for Advanced Oxygen Reduction in Acid Media Lai, Qingxue; Zheng, Lirong; Liang, Yanyu ACS Catalysis, Vol. 7, Issue 3 https://doi.org/10.1021/acscatal.6b02966	journal	February 2017
Unveiling Active Sites of CO ₂ Reduction on Nitrogen-Coordinated and Atomically Dispersed Iron and Cobalt Catalysts Pan, Fuping; Zhang, Hanguang; Liu, Kexi ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.8b00398	journal	March 2018
Highly Efficient Oxygen Reduction Reaction Electrocatalysts Synthesized under Nanospace Confinement of Metal–Organic Framework Guo, Jianing; Li, Yang; Cheng, Yuanhui ACS Nano, Vol. 11, Issue 8 https://doi.org/10.1021/acsnano.7b03807	journal	July 2017
Design and Synthesis of Bimetallic Electrocatalyst with Multilayered Pt-Skin Surfaces Wang, Chao; Chi, Miaofang; Li, Dongguo Journal of the American Chemical Society, Vol. 133, Issue 36, p. 14396-14403 https://doi.org/10.1021/ja2047655	journal	September 2011
Covalent Hybrid of Spinel Manganese–Cobalt Oxide and Graphene as Advanced Oxygen Reduction Electrocatalysts Liang, Yongye; Wang, Hailiang; Zhou, Jigang Journal of the American Chemical Society, Vol. 134, Issue 7 https://doi.org/10.1021/ja210924t	journal	February 2012
Strongly Coupled Inorganic/Nanocarbon Hybrid Materials for Advanced Electrocatalysis Liang, Yongye; Li, Yanguang; Wang, Hailiang Journal of the American Chemical Society, Vol. 135, Issue 6 https://doi.org/10.1021/ja3089923	journal	January 2013
Mesoporous Metal–Nitrogen-Doped Carbon Electrocatalysts for Highly Efficient Oxygen Reduction Reaction Liang, Hai-Wei; Wei, Wei; Wu, Zhong-Shuai Journal of the American Chemical Society, Vol. 135, Issue 43 https://doi.org/10.1021/ja407552k	journal	October 2013
Carbon Nanotube-Templated Synthesis of Covalent Porphyrin Network for Oxygen Reduction Reaction Hijazi, Ismail; Bourgeteau, Tiphaine; Cornut, Renaud Journal of the American Chemical Society, Vol. 136, Issue 17 https://doi.org/10.1021/ja500984k	journal	April 2014
Octahedral Pd@Pt _1.8 Ni Core–Shell Nanocrystals with Ultrathin PtNi Alloy Shells as Active Catalysts for Oxygen Reduction Reaction Zhao, Xu; Chen, Sheng; Fang, Zhicheng Journal of the American Chemical Society, Vol. 137, Issue 8 https://doi.org/10.1021/ja511596c	journal	February 2015
From Microporous Regular Frameworks to Mesoporous Materials with Ultrahigh Surface Area: Dynamic Reorganization of Porous Polymer Networks Kuhn, Pierre; Forget, Aurélien; Su, Dangsheng Journal of the American Chemical Society, Vol. 130, Issue 40 https://doi.org/10.1021/ja803708s	journal	October 2008
Noncovalent Immobilization of a Molecular Iron-Based Electrocatalyst on Carbon Electrodes for Selective, Efficient CO ₂ -to-CO Conversion in Water Maurin, Antoine; Robert, Marc Journal of the American Chemical Society, Vol. 138, Issue 8 https://doi.org/10.1021/jacs.5b12652	journal	February 2016
A General Approach to Preferential Formation of Active Fe–N _x Sites in Fe–N/C Electrocatalysts for Efficient Oxygen Reduction Reaction Sa, Young Jin; Seo, Dong-Jun; Woo, Jinwoo Journal of the American Chemical Society, Vol. 138, Issue 45 https://doi.org/10.1021/jacs.6b09470	journal	November 2016
Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu Journal of the American Chemical Society, Vol. 139, Issue 40 https://doi.org/10.1021/jacs.7b06514	journal	September 2017
Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt ₃ Ni and Pt ₃ Co Alloy Surfaces Stamenković, V.; Schmidt, T. J.; Ross, P. N. The Journal of Physical Chemistry B, Vol. 106, Issue 46 https://doi.org/10.1021/jp021182h	journal	November 2002
A New Fuel Cell Cathode Catalyst Jasinski, Raymond Nature, Vol. 201, Issue 4925, p. 1212-1213 https://doi.org/10.1038/2011212a0	journal	March 1964
Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells Proietti, Eric; Jaouen, Frédéric; Lefèvre, Michel Nature Communications, Vol. 2, Issue 1 https://doi.org/10.1038/ncomms1427	journal	August 2011
Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures Zhang, Xing; Wu, Zishan; Zhang, Xiao Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14675	journal	March 2017
Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst Cao, Ruiguo; Thapa, Ranjit; Kim, Hyejung Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3076	journal	June 2013
Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials Zitolo, Andrea; Goellner, Vincent; Armel, Vanessa Nature Materials, Vol. 14, Issue 9 https://doi.org/10.1038/nmat4367	journal	August 2015
A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai Nature Nanotechnology, Vol. 10, Issue 5 https://doi.org/10.1038/nnano.2015.48	journal	April 2015
Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2 Ju, Wen; Bagger, Alexander; Hao, Guang-Ping Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01035-z	journal	October 2017
Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction Weng, Zhe; Wu, Yueshen; Wang, Maoyu Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-02819-7	journal	January 2018
Scalable synthesis of bi-functional high-performance carbon nanotube sponge catalysts and electrodes with optimum C–N–Fe coordination for oxygen reduction reaction Yang, Gang; Choi, Woongchul; Pu, Xiong Energy & Environmental Science, Vol. 8, Issue 6 https://doi.org/10.1039/C5EE00682A	journal	January 2015
Structural and mechanistic basis for the high activity of Fe–N–C catalysts toward oxygen reduction Li, Jingkun; Ghoshal, Shraboni; Liang, Wentao Energy & Environmental Science, Vol. 9, Issue 7 https://doi.org/10.1039/C6EE01160H	journal	January 2016
SiO ₂ -protected shell mediated templating synthesis of Fe–N-doped carbon nanofibers and their enhanced oxygen reduction reaction performance Hu, Bi-Cheng; Wu, Zhen-Yu; Chu, Sheng-Qi Energy & Environmental Science, Vol. 11, Issue 8 https://doi.org/10.1039/C8EE00673C	journal	January 2018
The Achilles' heel of iron-based catalysts during oxygen reduction in an acidic medium Choi, Chang Hyuck; Lim, Hyung-Kyu; Chung, Min Wook Energy & Environmental Science, Vol. 11, Issue 11 https://doi.org/10.1039/C8EE01855C	journal	January 2018
Understanding the electrocatalysis of oxygen reduction on platinum and its alloys Stephens, Ifan E. L.; Bondarenko, Alexander S.; Grønbjerg, Ulrik Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee03590a	journal	January 2012
Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells Lefèvre, Michel; Proietti, Eric; Jaouen, Frédéric Science, Vol. 324, Issue 5923, p. 71-74 https://doi.org/10.1126/science.1170051	journal	April 2009
Combining theory and experiment in electrocatalysis: Insights into materials design Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F. Science, Vol. 355, Issue 6321 https://doi.org/10.1126/science.aad4998	journal	January 2017
Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst Chung, Hoon T.; Cullen, David A.; Higgins, Drew Science, Vol. 357, Issue 6350 https://doi.org/10.1126/science.aan2255	journal	August 2017
Elementary Mechanisms in Electrocatalysis: Revisiting the ORR Tafel Slope Holewinski, Adam; Linic, Suljo Journal of The Electrochemical Society, Vol. 159, Issue 11 https://doi.org/10.1149/2.022211jes	journal	January 2012

Cited By (1)

Magnetic purification of non-precious metal fuel cell catalysts for obtaining atomically dispersed Fe centers Nabae, Yuta; Nagata, Shinsuke; Kusaba, Keizo Catalysis Science & Technology, Vol. 10, Issue 2 https://doi.org/10.1039/c9cy02304f	journal	January 2020

Similar Records

Application of radioisotope techniques for the study of phthalocyanine catalyzed electrochemical processes in fuel cells

Journal Article · Wed Apr 20 23:00:00 EST 1977 · J. Phys. Chem.; (United States) · OSTI ID:7213551

Adsorption of ammonia on multilayer iron phthalocyanine

Journal Article · Mon Mar 21 00:00:00 EDT 2011 · Journal of Chemical Physics · OSTI ID:21560058

Molecular Fe-N₄ Moieties Coupled with Atomic Co-N₄ Sites Toward Improved Oxygen Reduction Performance

Journal Article · Wed Mar 27 20:00:00 EDT 2024 · Advanced Functional Materials · OSTI ID:2473653

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
carbon dioxide reduction reaction
iron phthalocyanine
oxygen reduction reaction
single-atom electrocatalysts
zeolitic imidazolate frameworks

Phthalocyanine Precursors To Construct Atomically Dispersed Iron Electrocatalysts

Citation Formats

References (52)

Cited By (1)

Similar Records

Related Subjects