Sacrificial Synthesis of Supported Ru Single Atoms and Clusters on N-doped Carbon Derived from Covalent Triazine Frameworks: A Charge Modulation Approach

Zihao Zhang; Siyu Yao; Xiaobing Hu; Francis Okejiri; Kun He; Pingying Liu; Ziqi Tian; Vinayak P. Dravid; Jie Fu; Xiang Zhu; Sheng Dai

doi:10.1002/advs.202001493

Sacrificial Synthesis of Supported Ru Single Atoms and Clusters on N-doped Carbon Derived from Covalent Triazine Frameworks: A Charge Modulation Approach

Zihao Zhang, Siyu Yao, Xiaobing Hu, Francis Okejiri, Kun He, Pingying Liu, Ziqi Tian, Vinayak P. Dravid, Jie Fu, Xiang Zhu, Sheng Dai

Chemical Sciences Division

Research output: Contribution to journal › Article › peer-review

46 Scopus citations

Abstract

High-temperature pyrolysis of nitrogen (N)-rich, crystalline porous organic architectures in the presence of a metal precursor is an important chemical process in heterogeneous catalysis for the fabrication of highly porous N-carbon-supported metal catalysts. Herein, covalent triazine framework (CTF) and CTF-I (that is, CTF after charge modulation with iodomethane) are presented as sacrificial templates, for the synthesis of carbon-supported Ru catalysts—Ru-CTF-900 and Ru-CTF-I-900 respectively, following high-temperature pyrolysis at 900 °C under N₂ atmosphere. Predictably, the dispersed Ru on pristine CTF carrier suffered severe sintering of the Ru nanoparticles (NPs) during heat treatment at 900 °C. However, the Ru-CTF-I-900 catalyst is composed of ultra-small Ru NPs and abundant Ru single atoms which may have resulted from much stronger Ru-N interactions. Through modification of the micro-environment within the CTF architecture, Ru precursor interacted on charged-modulated CTF framework shows electrostatic repulsion and steric hindrance, thus contributing toward the high density of single Ru atoms and even smaller Ru NPs after pyrolysis. A Ru-Ru coordination number of only 1.3 is observed in the novel Ru-CTF-I-900 catalyst, which exhibits significantly higher catalytic activity than Ru-CTF-900 for transfer hydrogenation of acetophenone.

Original language	English
Article number	2001493
Journal	Advanced Science
Volume	8
Issue number	3
DOIs	https://doi.org/10.1002/advs.202001493
State	Published - Feb 3 2021

Funding

F.O. and S.D. were sponsored by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science program. J.F. was supported by the National Natural Science Foundation of China (no. 21978259; no. 22022812), the Zhejiang Provincial Natural Science Foundation of China (no. LR17B060002), and the Fundamental Research Funds for the Central Universities. This research used resources of the 8‐ID beamline of the National Synchrotron Light Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE‐AC02‐98CH10886. This work made use of the EPIC facility of Northwestern University’s NU Center, which has received support from the SHyNE Resource (NSF ECCS‐2025633), the IIN, and Northwestern's MRSEC program (NSF DMR‐1720139). ANCE

Funders	Funder number
SHyNE Resource	NSF DMR‐1720139, ECCS‐2025633
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Brookhaven National Laboratory	DE‐AC02‐98CH10886
Brookhaven National Laboratory
Northwestern University
National Natural Science Foundation of China	21978259, 22022812
National Natural Science Foundation of China
Natural Science Foundation of Zhejiang Province	LR17B060002
Natural Science Foundation of Zhejiang Province
Fundamental Research Funds for the Central Universities

Keywords

N-doped carbon
charge modulation
covalent triazine frameworks
sintering-resistance

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10.1002/advs.202001493

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title = "Sacrificial Synthesis of Supported Ru Single Atoms and Clusters on N-doped Carbon Derived from Covalent Triazine Frameworks: A Charge Modulation Approach",

abstract = "High-temperature pyrolysis of nitrogen (N)-rich, crystalline porous organic architectures in the presence of a metal precursor is an important chemical process in heterogeneous catalysis for the fabrication of highly porous N-carbon-supported metal catalysts. Herein, covalent triazine framework (CTF) and CTF-I (that is, CTF after charge modulation with iodomethane) are presented as sacrificial templates, for the synthesis of carbon-supported Ru catalysts—Ru-CTF-900 and Ru-CTF-I-900 respectively, following high-temperature pyrolysis at 900 °C under N2 atmosphere. Predictably, the dispersed Ru on pristine CTF carrier suffered severe sintering of the Ru nanoparticles (NPs) during heat treatment at 900 °C. However, the Ru-CTF-I-900 catalyst is composed of ultra-small Ru NPs and abundant Ru single atoms which may have resulted from much stronger Ru-N interactions. Through modification of the micro-environment within the CTF architecture, Ru precursor interacted on charged-modulated CTF framework shows electrostatic repulsion and steric hindrance, thus contributing toward the high density of single Ru atoms and even smaller Ru NPs after pyrolysis. A Ru-Ru coordination number of only 1.3 is observed in the novel Ru-CTF-I-900 catalyst, which exhibits significantly higher catalytic activity than Ru-CTF-900 for transfer hydrogenation of acetophenone.",

keywords = "N-doped carbon, charge modulation, covalent triazine frameworks, sintering-resistance",

author = "Zihao Zhang and Siyu Yao and Xiaobing Hu and Francis Okejiri and Kun He and Pingying Liu and Ziqi Tian and Dravid, {Vinayak P.} and Jie Fu and Xiang Zhu and Sheng Dai",

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T1 - Sacrificial Synthesis of Supported Ru Single Atoms and Clusters on N-doped Carbon Derived from Covalent Triazine Frameworks

T2 - A Charge Modulation Approach

AU - Zhang, Zihao

AU - Yao, Siyu

AU - Hu, Xiaobing

AU - Okejiri, Francis

AU - He, Kun

AU - Liu, Pingying

AU - Tian, Ziqi

AU - Dravid, Vinayak P.

AU - Fu, Jie

AU - Zhu, Xiang

AU - Dai, Sheng

PY - 2021/2/3

Y1 - 2021/2/3

N2 - High-temperature pyrolysis of nitrogen (N)-rich, crystalline porous organic architectures in the presence of a metal precursor is an important chemical process in heterogeneous catalysis for the fabrication of highly porous N-carbon-supported metal catalysts. Herein, covalent triazine framework (CTF) and CTF-I (that is, CTF after charge modulation with iodomethane) are presented as sacrificial templates, for the synthesis of carbon-supported Ru catalysts—Ru-CTF-900 and Ru-CTF-I-900 respectively, following high-temperature pyrolysis at 900 °C under N2 atmosphere. Predictably, the dispersed Ru on pristine CTF carrier suffered severe sintering of the Ru nanoparticles (NPs) during heat treatment at 900 °C. However, the Ru-CTF-I-900 catalyst is composed of ultra-small Ru NPs and abundant Ru single atoms which may have resulted from much stronger Ru-N interactions. Through modification of the micro-environment within the CTF architecture, Ru precursor interacted on charged-modulated CTF framework shows electrostatic repulsion and steric hindrance, thus contributing toward the high density of single Ru atoms and even smaller Ru NPs after pyrolysis. A Ru-Ru coordination number of only 1.3 is observed in the novel Ru-CTF-I-900 catalyst, which exhibits significantly higher catalytic activity than Ru-CTF-900 for transfer hydrogenation of acetophenone.

AB - High-temperature pyrolysis of nitrogen (N)-rich, crystalline porous organic architectures in the presence of a metal precursor is an important chemical process in heterogeneous catalysis for the fabrication of highly porous N-carbon-supported metal catalysts. Herein, covalent triazine framework (CTF) and CTF-I (that is, CTF after charge modulation with iodomethane) are presented as sacrificial templates, for the synthesis of carbon-supported Ru catalysts—Ru-CTF-900 and Ru-CTF-I-900 respectively, following high-temperature pyrolysis at 900 °C under N2 atmosphere. Predictably, the dispersed Ru on pristine CTF carrier suffered severe sintering of the Ru nanoparticles (NPs) during heat treatment at 900 °C. However, the Ru-CTF-I-900 catalyst is composed of ultra-small Ru NPs and abundant Ru single atoms which may have resulted from much stronger Ru-N interactions. Through modification of the micro-environment within the CTF architecture, Ru precursor interacted on charged-modulated CTF framework shows electrostatic repulsion and steric hindrance, thus contributing toward the high density of single Ru atoms and even smaller Ru NPs after pyrolysis. A Ru-Ru coordination number of only 1.3 is observed in the novel Ru-CTF-I-900 catalyst, which exhibits significantly higher catalytic activity than Ru-CTF-900 for transfer hydrogenation of acetophenone.

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KW - covalent triazine frameworks

KW - sintering-resistance

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Sacrificial Synthesis of Supported Ru Single Atoms and Clusters on N-doped Carbon Derived from Covalent Triazine Frameworks: A Charge Modulation Approach

Abstract

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Keywords

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