Atomically dispersed nickel as coke-resistant active sites for methane dry reforming

Mohcin Akri; Shu Zhao; Xiaoyu Li; Ketao Zang; Adam F Lee; Mark A Isaacs; Wei Xi; Yuvaraj Gangarajula; Jun Luo; Yujing Ren; Yi-Tao Cui; Lei Li; Yang Su; Xiaoli Pan; Wu Wen; Yang Pan; Karen Wilson; Lin Li; Botao Qiao; Hirofumi Ishii; Yen-Fa Liao; Aiqin Wang; Xiaodong Wang; Tao Zhang

doi:10.1038/s41467-019-12843-w

Atomically dispersed nickel as coke-resistant active sites for methane dry reforming

Nat Commun. 2019 Nov 15;10(1):5181. doi: 10.1038/s41467-019-12843-w.

Authors

Mohcin Akri¹, Shu Zhao², Xiaoyu Li^{1

3}, Ketao Zang⁴, Adam F Lee⁵, Mark A Isaacs⁶, Wei Xi⁴, Yuvaraj Gangarajula¹, Jun Luo⁴, Yujing Ren¹, Yi-Tao Cui⁷, Lei Li⁸, Yang Su¹, Xiaoli Pan¹, Wu Wen⁹, Yang Pan⁹, Karen Wilson⁵, Lin Li¹, Botao Qiao^{10

11}, Hirofumi Ishii¹², Yen-Fa Liao¹², Aiqin Wang¹, Xiaodong Wang¹, Tao Zhang^{13

14}

Affiliations

¹ CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy Sciences, 116023, Dalian, China.
² Beijing Guyue New Materials Research Institute, Beijing University of Technology, 100124, Beijing, China.
³ University of Chinese Academy of Sciences, 100049, Beijing, China.
⁴ Center for Electron Microscopy and Tianjin Key Lab of Advanced Functional Porous Materials, Institute for New Energy Materials, School of Materials Science and Engineering, Tianjin University of Technology, 300384, Tianjin, China.
⁵ Applied Chemistry & Environmental Science, RMIT University, Melbourne, 3000, Australia.
⁶ Department of Chemistry, University College London, London, UK.
⁷ Synchrotron Radiation Laboratory, Laser and Synchrotron Research Center (LASOR), The Institute for Solid State Physics, The University of Tokyo, 1-490-2 Kouto, Shingu-cho Tatsuno, Hyogo, 679-5165, Japan.
⁸ Synchrotron Radiation Research Center, Hyogo Science and Technology Association, Hyogo, 679-5165, Japan.
⁹ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, China.
¹⁰ CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy Sciences, 116023, Dalian, China. bqiao@dicp.ac.cn.
¹¹ Dalian National Laboratory for Clean Energy, 116023, Dalian, China. bqiao@dicp.ac.cn.
¹² National Synchrotron Radiation Research Center, Hsinchu, 30076, Taiwan (ROC).
¹³ CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy Sciences, 116023, Dalian, China. taozhang@dicp.ac.cn.
¹⁴ University of Chinese Academy of Sciences, 100049, Beijing, China. taozhang@dicp.ac.cn.

Abstract

Dry reforming of methane (DRM) is an attractive route to utilize CO₂ as a chemical feedstock with which to convert CH₄ into valuable syngas and simultaneously mitigate both greenhouse gases. Ni-based DRM catalysts are promising due to their high activity and low cost, but suffer from poor stability due to coke formation which has hindered their commercialization. Herein, we report that atomically dispersed Ni single atoms, stabilized by interaction with Ce-doped hydroxyapatite, are highly active and coke-resistant catalytic sites for DRM. Experimental and computational studies reveal that isolated Ni atoms are intrinsically coke-resistant due to their unique ability to only activate the first C-H bond in CH₄, thus avoiding methane deep decomposition into carbon. This discovery offers new opportunities to develop large-scale DRM processes using earth abundant catalysts.

Publication types

Research Support, Non-U.S. Gov't