DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Nanocasting SiO2 into metal–organic frameworks imparts dual protection to high-loading Fe single-atom electrocatalysts

Abstract

Single-atom catalysts (SACs) have sparked broad interest recently while the low metal loading poses a big challenge for further applications. Herein, a dual protection strategy has been developed to give high-content SACs by nanocasting SiO2 into porphyrinic metal–organic frameworks (MOFs). The pyrolysis of SiO2@MOF composite affords singleatom Fe implanted N-doped porous carbon (FeSA–N–C) with high Fe loading (3.46 wt%). The spatial isolation of Fe atoms centered in porphyrin linkers of MOF sets the first protective barrier to inhibit the Fe agglomeration during pyrolysis. The SiO2 in MOF provides additional protection by creating thermally stable FeN4/SiO2 interfaces. Thanks to the high-density FeSA sites, FeSA–N–C demonstrates excellent oxygen reduction performance in both alkaline and acidic medias. Meanwhile, FeSA–N–C also exhibits encouraging performance in proton exchange membrane fuel cell, demonstrating great potential for practical application. More far-reaching, this work grants a general synthetic methodology toward high-content SACs (such as FeSA, CoSA, NiSA). https://doi.org/10.1038/s41467-020-16715-6 OPEN 1

Authors:
 [1];  [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Science and Technology of China, Hefei (China)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. North China Electric Power Univ., Baoding(China)
  4. Beihang Univ. (China)
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1632832
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Jiao, Long, Zhang, Rui, Wan, Gang, Yang, Weijie, Wan, Xin, Zhou, Hua, Shui, Jianglan, Yu, Shu-Hong, and Jiang, Hai-Long. Nanocasting SiO2 into metal–organic frameworks imparts dual protection to high-loading Fe single-atom electrocatalysts. United States: N. p., 2020. Web. doi:10.1038/s41467-020-16715-6.
Jiao, Long, Zhang, Rui, Wan, Gang, Yang, Weijie, Wan, Xin, Zhou, Hua, Shui, Jianglan, Yu, Shu-Hong, & Jiang, Hai-Long. Nanocasting SiO2 into metal–organic frameworks imparts dual protection to high-loading Fe single-atom electrocatalysts. United States. https://doi.org/10.1038/s41467-020-16715-6
Jiao, Long, Zhang, Rui, Wan, Gang, Yang, Weijie, Wan, Xin, Zhou, Hua, Shui, Jianglan, Yu, Shu-Hong, and Jiang, Hai-Long. Fri . "Nanocasting SiO2 into metal–organic frameworks imparts dual protection to high-loading Fe single-atom electrocatalysts". United States. https://doi.org/10.1038/s41467-020-16715-6. https://www.osti.gov/servlets/purl/1632832.
@article{osti_1632832,
title = {Nanocasting SiO2 into metal–organic frameworks imparts dual protection to high-loading Fe single-atom electrocatalysts},
author = {Jiao, Long and Zhang, Rui and Wan, Gang and Yang, Weijie and Wan, Xin and Zhou, Hua and Shui, Jianglan and Yu, Shu-Hong and Jiang, Hai-Long},
abstractNote = {Single-atom catalysts (SACs) have sparked broad interest recently while the low metal loading poses a big challenge for further applications. Herein, a dual protection strategy has been developed to give high-content SACs by nanocasting SiO2 into porphyrinic metal–organic frameworks (MOFs). The pyrolysis of SiO2@MOF composite affords singleatom Fe implanted N-doped porous carbon (FeSA–N–C) with high Fe loading (3.46 wt%). The spatial isolation of Fe atoms centered in porphyrin linkers of MOF sets the first protective barrier to inhibit the Fe agglomeration during pyrolysis. The SiO2 in MOF provides additional protection by creating thermally stable FeN4/SiO2 interfaces. Thanks to the high-density FeSA sites, FeSA–N–C demonstrates excellent oxygen reduction performance in both alkaline and acidic medias. Meanwhile, FeSA–N–C also exhibits encouraging performance in proton exchange membrane fuel cell, demonstrating great potential for practical application. More far-reaching, this work grants a general synthetic methodology toward high-content SACs (such as FeSA, CoSA, NiSA). https://doi.org/10.1038/s41467-020-16715-6 OPEN 1},
doi = {10.1038/s41467-020-16715-6},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United States},
year = {Fri Jun 05 00:00:00 EDT 2020},
month = {Fri Jun 05 00:00:00 EDT 2020}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 220 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: Schematic illustration. Illustration showing the nanocasting-assisted fabrication of FeSA–N–C from PCN-222(Fe).

Save / Share:

Works referenced in this record:

General Oriented Formation of Carbon Nanotubes from Metal–Organic Frameworks
journal, June 2017

  • Meng, Jiashen; Niu, Chaojiang; Xu, Linhan
  • Journal of the American Chemical Society, Vol. 139, Issue 24
  • DOI: 10.1021/jacs.7b01942

Efficient Oxygen Reduction Reaction (ORR) Catalysts Based on Single Iron Atoms Dispersed on a Hierarchically Structured Porous Carbon Framework
journal, June 2018

  • Zhang, Zhengping; Sun, Junting; Wang, Feng
  • Angewandte Chemie International Edition, Vol. 57, Issue 29
  • DOI: 10.1002/anie.201804958

Postsynthetic Tuning of Metal–Organic Frameworks for Targeted Applications
journal, February 2017


Graphene Defects Trap Atomic Ni Species for Hydrogen and Oxygen Evolution Reactions
journal, February 2018


Carbon-Rich Nanomaterials: Fascinating Hydrogen and Oxygen Electrocatalysts
journal, July 2018

  • Zhang, Jian; Chen, Guangbo; Müllen, Klaus
  • Advanced Materials, Vol. 30, Issue 40
  • DOI: 10.1002/adma.201800528

Single cobalt sites in mesoporous N-doped carbon matrix for selective catalytic hydrogenation of nitroarenes
journal, January 2018


Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks
journal, June 2012

  • Morris, William; Volosskiy, Boris; Demir, Selcuk
  • Inorganic Chemistry, Vol. 51, Issue 12, p. 6443-6445
  • DOI: 10.1021/ic300825s

Catalysis by Supported Single Metal Atoms
journal, November 2016


Single-Atom Catalysts: Synthetic Strategies and Electrochemical Applications
journal, July 2018


Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation
journal, September 2017

  • Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu
  • Journal of the American Chemical Society, Vol. 139, Issue 40
  • DOI: 10.1021/jacs.7b06514

Metal–Organic Framework Derived Hybrid Co 3 O 4 -Carbon Porous Nanowire Arrays as Reversible Oxygen Evolution Electrodes
journal, September 2014

  • Ma, Tian Yi; Dai, Sheng; Jaroniec, Mietek
  • Journal of the American Chemical Society, Vol. 136, Issue 39
  • DOI: 10.1021/ja5082553

Single-Atom Electrocatalysts
journal, October 2017

  • Zhu, Chengzhou; Fu, Shaofang; Shi, Qiurong
  • Angewandte Chemie International Edition, Vol. 56, Issue 45
  • DOI: 10.1002/anie.201703864

A General Approach to Preferential Formation of Active Fe–N x Sites in Fe–N/C Electrocatalysts for Efficient Oxygen Reduction Reaction
journal, November 2016

  • Sa, Young Jin; Seo, Dong-Jun; Woo, Jinwoo
  • Journal of the American Chemical Society, Vol. 138, Issue 45
  • DOI: 10.1021/jacs.6b09470

Phenylenediamine-Based FeN x /C Catalyst with High Activity for Oxygen Reduction in Acid Medium and Its Active-Site Probing
journal, July 2014

  • Wang, Qiang; Zhou, Zhi-You; Lai, Yu-Jiao
  • Journal of the American Chemical Society, Vol. 136, Issue 31
  • DOI: 10.1021/ja505777v

Metal-Organic Frameworks Encapsulating Active Nanoparticles as Emerging Composites for Catalysis: Recent Progress and Perspectives
journal, September 2018


Highly Active and Stable Single-Atom Cu Catalysts Supported by a Metal–Organic Framework
journal, March 2019

  • Abdel-Mageed, Ali M.; Rungtaweevoranit, Bunyarat; Parlinska-Wojtan, Magdalena
  • Journal of the American Chemical Society, Vol. 141, Issue 13
  • DOI: 10.1021/jacs.8b11386

Isolated Single Iron Atoms Anchored on N-Doped Porous Carbon as an Efficient Electrocatalyst for the Oxygen Reduction Reaction
journal, April 2017

  • Chen, Yuanjun; Ji, Shufang; Wang, Yanggang
  • Angewandte Chemie International Edition, Vol. 56, Issue 24
  • DOI: 10.1002/anie.201702473

Harnessing the Wisdom in Colloidal Chemistry to Make Stable Single-Atom Catalysts
journal, July 2018

  • Hülsey, Max J.; Zhang, Jiaguang; Yan, Ning
  • Advanced Materials, Vol. 30, Issue 47
  • DOI: 10.1002/adma.201802304

Metal–Organic Frameworks (MOFs)
journal, January 2014

  • Zhou, Hong-Cai “Joe”; Kitagawa, Susumu
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS90059F

Synthesis of Supported Ultrafine Non-noble Subnanometer-Scale Metal Particles Derived from Metal-Organic Frameworks as Highly Efficient Heterogeneous Catalysts
journal, November 2015

  • Kang, Xinchen; Liu, Huizhen; Hou, Minqiang
  • Angewandte Chemie International Edition, Vol. 55, Issue 3
  • DOI: 10.1002/anie.201508107

Silica-Protected Ultrathin Ni 3 FeN Nanocatalyst for the Efficient Hydrolytic Dehydrogenation of NH 3 BH 3
journal, January 2018

  • Zhang, Xin; Zhao, Yufei; Jia, Xiaodan
  • Advanced Energy Materials, Vol. 8, Issue 12
  • DOI: 10.1002/aenm.201702780

Metal-Organic Frameworks for Separation
journal, March 2018

  • Zhao, Xiang; Wang, Yanxiang; Li, Dong-Sheng
  • Advanced Materials, Vol. 30, Issue 37
  • DOI: 10.1002/adma.201705189

Metal-Organic-Framework-Based Single-Atom Catalysts for Energy Applications
journal, April 2019


Metal-Organic Frameworks as Platforms for Catalytic Applications
journal, November 2017


Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis
journal, April 2013

  • Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300361m

Emerging Multifunctional Metal-Organic Framework Materials
journal, July 2016


Understanding the High Activity of Fe–N–C Electrocatalysts in Oxygen Reduction: Fe/Fe 3 C Nanoparticles Boost the Activity of Fe–N x
journal, March 2016

  • Jiang, Wen-Jie; Gu, Lin; Li, Li
  • Journal of the American Chemical Society, Vol. 138, Issue 10
  • DOI: 10.1021/jacs.6b00757

Edge-Site Engineering of Atomically Dispersed Fe–N 4 by Selective C–N Bond Cleavage for Enhanced Oxygen Reduction Reaction Activities
journal, August 2018

  • Jiang, Rui; Li, Li; Sheng, Tian
  • Journal of the American Chemical Society, Vol. 140, Issue 37
  • DOI: 10.1021/jacs.8b07294

Photochemical route for synthesizing atomically dispersed palladium catalysts
journal, May 2016


Thermal Stabilization of Metal–Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting
journal, February 2016

  • Malonzo, Camille D.; Shaker, Sammy M.; Ren, Limin
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.5b12688

Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles
journal, April 2018


Metal–organic framework-derived porous materials for catalysis
journal, May 2018


From Metal-Organic Frameworks to Single-Atom Fe Implanted N-doped Porous Carbons: Efficient Oxygen Reduction in Both Alkaline and Acidic Media
journal, June 2018

  • Jiao, Long; Wan, Gang; Zhang, Rui
  • Angewandte Chemie International Edition, Vol. 57, Issue 28
  • DOI: 10.1002/anie.201803262

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Biomimetic Catalysis of a Porous Iron-Based Metal–Metalloporphyrin Framework
journal, November 2012

  • Chen, Yao; Hoang, Tran; Ma, Shengqian
  • Inorganic Chemistry, Vol. 51, Issue 23
  • DOI: 10.1021/ic301923x

Atomically dispersed Fe 3+ sites catalyze efficient CO 2 electroreduction to CO
journal, June 2019


Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts
journal, August 2016

  • Yin, Peiqun; Yao, Tao; Wu, Yuen
  • Angewandte Chemie International Edition, Vol. 55, Issue 36
  • DOI: 10.1002/anie.201604802

Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts
journal, August 2012

  • Feng, Dawei; Gu, Zhi-Yuan; Li, Jian-Rong
  • Angewandte Chemie International Edition, Vol. 51, Issue 41
  • DOI: 10.1002/anie.201204475

Covalent Hybrid of Spinel Manganese–Cobalt Oxide and Graphene as Advanced Oxygen Reduction Electrocatalysts
journal, February 2012

  • Liang, Yongye; Wang, Hailiang; Zhou, Jigang
  • Journal of the American Chemical Society, Vol. 134, Issue 7
  • DOI: 10.1021/ja210924t

Single-Atom Catalysts: Emerging Multifunctional Materials in Heterogeneous Catalysis
journal, September 2017


Dynamic traction of lattice-confined platinum atoms into mesoporous carbon matrix for hydrogen evolution reaction
journal, January 2018


A universal principle for a rational design of single-atom electrocatalysts
journal, April 2018


Oriented electron transmission in polyoxometalate-metalloporphyrin organic framework for highly selective electroreduction of CO2
journal, October 2018


Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction
journal, September 2014

  • Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5973

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.