Balancing elementary steps enables coke-free dry reforming of methane

Yu, Jiaqi; Le, Tien; Jing, Dapeng; Stavitski, Eli; Hunter, Nicholas; Lalit, Kanika; Leshchev, Denis; Resasco, Daniel E.; Sargent, Edward H.; Wang, Bin; Huang, Wenyu

doi:10.1038/s41467-023-43277-0

Title: Balancing elementary steps enables coke-free dry reforming of methane

Journal Article · 18 November 2023 · Nature Communications

DOI: https://doi.org/10.1038/s41467-023-43277-0 · OSTI ID:2282139

^[1];

^[2];

^[3];

^[4]; Hunter, Nicholas ^[3]; Lalit, Kanika ^[3]; Leshchev, Denis ^[4];

^[2];

^[5];

^[2];

^[3]

Northwestern University, Evanston, IL (United States); Iowa State University, Ames, IA (United States)
University of Oklahoma, Norman, OK (United States)
Iowa State University, Ames, IA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Northwestern University, Evanston, IL (United States)

Balancing kinetics, a crucial priority in catalysis, is frequently achieved by sacrificing activity of elementary steps to suppress side reactions and enhance catalyst stability. Dry reforming of methane (DRM), a process operated at high temperature, usually involves fast C-H activation but sluggish carbon removal, resulting in coke deposition and catalyst deactivation. Studies focused solely on catalyst innovation are insufficient in addressing coke formation efficiently. Herein, we develop coke-free catalysts that balance kinetics of elementary steps for overall thermodynamics optimization. Beginning from a highly active cobalt aluminum oxide (CoAl₂O₄) catalyst that is susceptible to severe coke formation, we substitute aluminum (Al) with gallium (Ga), reporting a CoAl_0.5Ga_1.5O₄-R catalyst that performs DRM stably over 1000 hours without observable coke deposition. We find that Ga enhances DRM stability by suppressing C-H activation to balance carbon removal. A series of coke-free DRM catalysts are developed herein by partially substituting Al from CoAl₂O₄ with other metals.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Univ. of Oklahoma, Norman, OK (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704; SC0020300; CHE-2108306/2108307; ECCS-2025633; DMR-1720139

OSTI ID:: 2282139

Report Number(s):: BNL-225226-2024-JAAM

Journal Information:: Nature Communications, Vol. 14, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Ni–Mg Supported Catalysts on Low-Temperature Electrocatalytic Tri-reforming of Methane with Suppressed Oxidation Yabe, Tomohiro; Yamada, Kensei; Oguri, Task ACS Catalysis, Vol. 8, Issue 12 https://doi.org/10.1021/acscatal.8b02476	journal	October 2018
Dry reforming of methane by stable Ni–Mo nanocatalysts on single-crystalline MgO Song, Youngdong; Ozdemir, Ercan; Ramesh, Sreerangappa Science, Vol. 367, Issue 6479 https://doi.org/10.1126/science.aav2412	journal	February 2020
Strong coke-resistivity of spherical hollow Ni/SiO2 catalysts with shell-confined high-content Ni nanoparticles for methane dry reforming with CO2 Kosari, Mohammadreza; Askari, Saeed; Seayad, Abdul Majeed Applied Catalysis B: Environmental, Vol. 310 https://doi.org/10.1016/j.apcatb.2022.121360	journal	August 2022
Ni/Ce0.9Eu0.1O1.95 with enhanced coke resistance for dry reforming of methane Wang, Yaning; Zhang, Rongjun; Yan, Binhang Journal of Catalysis, Vol. 407 https://doi.org/10.1016/j.jcat.2022.01.020	journal	March 2022
C–H bond activation in light alkanes: a theoretical perspective Wang, Yalan; Hu, Ping; Yang, Jia Chemical Society Reviews, Vol. 50, Issue 7 https://doi.org/10.1039/D0CS01262A	journal	January 2021
Synergy of Single-Atom Ni ₁ and Ru ₁ Sites on CeO ₂ for Dry Reforming of CH ₄ Tang, Yu; Wei, Yuechang; Wang, Ziyun Journal of the American Chemical Society, Vol. 141, Issue 18 https://doi.org/10.1021/jacs.8b10910	journal	April 2019
Silica‐Enveloped 2D‐Sheet‐to‐Nanocrystals Conversion for Resilient Catalytic Dry Reforming of Methane Jang, Sun Woo; Dutta, Soumen; Kumar, Amit Small, Vol. 17, Issue 34 https://doi.org/10.1002/smll.202102851	journal	July 2021
Embedding high loading and uniform Ni nanoparticles into silicalite-1 zeolite for dry reforming of methane Liu, Yang; Chen, Yong; Gao, Zirui Applied Catalysis B: Environmental, Vol. 307 https://doi.org/10.1016/j.apcatb.2022.121202	journal	June 2022
One-step synthesis of ordered mesoporous CoAl ₂ O ₄ spinel-based metal oxides for CO ₂ reforming of CH ₄ Xu, Leilei; Zhang, Jian; Wang, Fagen RSC Advances, Vol. 5, Issue 60 https://doi.org/10.1039/C5RA07249B	journal	January 2015
Zeolite fixed cobalt–nickel nanoparticles for coking and sintering resistance in dry reforming of methane Zhu, Qiuyan; Liu, Yifeng; Qin, Xuedi Chemical Engineering Science, Vol. 280 https://doi.org/10.1016/j.ces.2023.119030	journal	October 2023
A heterogeneous single Cu catalyst of Cu atoms confined in the spinel lattice of MgAl ₂ O ₄ with good catalytic activity and stability for NO reduction by CO Wu, Jichun; Li, Yuanzhi; Yang, Yi Journal of Materials Chemistry A, Vol. 7, Issue 12 https://doi.org/10.1039/C8TA11528A	journal	January 2019
Double-Site Doping of a V Promoter on Ni _x -V-MgAl Catalysts for the DRM Reaction: Simultaneous Effect on CH ₄ and CO ₂ Activation Lu, Yao; Kang, Li; Guo, Dan ACS Catalysis, Vol. 11, Issue 14 https://doi.org/10.1021/acscatal.1c01299	journal	July 2021
Catalyst design for dry reforming of methane: Analysis review Aramouni, Nicolas Abdel Karim; Touma, Jad G.; Tarboush, Belal Abu Renewable and Sustainable Energy Reviews, Vol. 82 https://doi.org/10.1016/j.rser.2017.09.076	journal	February 2018
Thermodynamic Analysis of Dry Reforming of Methane for Valorization of Landfill Gas and Natural Gas Jensen, Christopher; Duyar, Melis S. Energy Technology, Vol. 9, Issue 7 https://doi.org/10.1002/ente.202100106	journal	May 2021
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Silica–Ceria sandwiched Ni core–shell catalyst for low temperature dry reforming of biogas: Coke resistance and mechanistic insights Das, S.; Ashok, J.; Bian, Z. Applied Catalysis B: Environmental, Vol. 230 https://doi.org/10.1016/j.apcatb.2018.02.041	journal	August 2018
Atomically dispersed nickel as coke-resistant active sites for methane dry reforming Akri, Mohcin; Zhao, Shu; Li, Xiaoyu Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12843-w	journal	November 2019
Crystallographic Dependence of CO Activation on Cobalt Catalysts: HCP versus FCC Liu, Jin-Xun; Su, Hai-Yan; Sun, Da-Peng Journal of the American Chemical Society, Vol. 135, Issue 44 https://doi.org/10.1021/ja408521w	journal	October 2013
Cooperatively enhanced coking resistance via boron nitride coating over Ni-based catalysts for dry reforming of methane Deng, Jiang; Bu, Kankan; Shen, Yongjie Applied Catalysis B: Environmental, Vol. 302 https://doi.org/10.1016/j.apcatb.2021.120859	journal	March 2022
Photocatalytic uphill conversion of natural gas beyond the limitation of thermal reaction systems Shoji, Shusaku; Peng, Xiaobo; Yamaguchi, Akira Nature Catalysis, Vol. 3, Issue 2 https://doi.org/10.1038/s41929-019-0419-z	journal	January 2020
Role of the nanoparticles of Cu-Co alloy derived from perovskite in dry reforming of methane Touahra, Fouzia; Chebout, Redouane; Lerari, Djahida Energy, Vol. 171 https://doi.org/10.1016/j.energy.2019.01.085	journal	March 2019
Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios Song, Chunshan; Pan, Wei Catalysis Today, Vol. 98, Issue 4 https://doi.org/10.1016/j.cattod.2004.09.054	journal	December 2004
Enhanced CO2 utilization in dry reforming of methane achieved through nickel-mediated hydrogen spillover in zeolite crystals Zhu, Qiuyan; Zhou, Hang; Wang, Liang Nature Catalysis, Vol. 5, Issue 11 https://doi.org/10.1038/s41929-022-00870-8	journal	November 2022
Reaction-Induced Strong Metal–Support Interactions between Metals and Inert Boron Nitride Nanosheets Dong, Jinhu; Fu, Qiang; Li, Haobo Journal of the American Chemical Society, Vol. 142, Issue 40 https://doi.org/10.1021/jacs.0c08139	journal	September 2020
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Hydrotalcite-derived Co/Mg(Al)O as a stable and coke-resistant catalyst for low-temperature carbon dioxide reforming of methane Li, Dalin; Xu, Shuping; Song, Kai Applied Catalysis A: General, Vol. 552 https://doi.org/10.1016/j.apcata.2017.12.022	journal	February 2018
Dry reforming of methane over the cobalt catalyst: Theoretical insights into the reaction kinetics and mechanism for catalyst deactivation Chen, Shuyue; Zaffran, Jeremie; Yang, Bo Applied Catalysis B: Environmental, Vol. 270 https://doi.org/10.1016/j.apcatb.2020.118859	journal	August 2020
Consequences of Surface Oxophilicity of Ni, Ni-Co, and Co Clusters on Methane Activation Tu, Weifeng; Ghoussoub, Mireille; Singh, Chandra Veer Journal of the American Chemical Society, Vol. 139, Issue 20 https://doi.org/10.1021/jacs.7b01632	journal	May 2017
Promoting Methane Dry Reforming over Ni Catalysts via Modulating Surface Electronic Structures of BN Supports by Doping Carbon Zhang, Xiaoyu; Deng, Jiang; Lan, Tianwei ACS Catalysis, Vol. 12, Issue 22 https://doi.org/10.1021/acscatal.2c04800	journal	November 2022
Kinetic Assessment of the Dry Reforming of Methane over a Ni–La₂O₃Catalyst Sandoval-Bohórquez, Víctor Stivenson; Morales-Valencia, Edgar M.; Castillo-Araiza, Carlos O. ACS Catalysis, Vol. 11, Issue 18 https://doi.org/10.1021/acscatal.1c02631	journal	September 2021
Facile synthesis of multi-layered nanostructured Ni/CeO2 catalyst plus in-situ pre-treatment for efficient dry reforming of methane Zhou, Rufan; Mohamedali, Mohanned; Ren, Yuxuan Applied Catalysis B: Environmental, Vol. 316 https://doi.org/10.1016/j.apcatb.2022.121696	journal	November 2022
Catalytic reforming of methane with H2S via dynamically stabilized sulfur on transition metal oxides and sulfides Wang, Yong; Chen, Xiaofeng; Shi, Hui Nature Catalysis, Vol. 6, Issue 2 https://doi.org/10.1038/s41929-023-00922-7	journal	February 2023
Light-driven methane dry reforming with single atomic site antenna-reactor plasmonic photocatalysts Zhou, Linan; Martirez, John Mark P.; Finzel, Jordan Nature Energy, Vol. 5, Issue 1 https://doi.org/10.1038/s41560-019-0517-9	journal	January 2020
Methane Oxyforming for Synthesis Gas Production York, Andrew P. E.; Xiao, Tian‐cun; Green, Malcolm L. H. Catalysis Reviews, Vol. 49, Issue 4 https://doi.org/10.1080/01614940701583315	journal	October 2007
A review of dry (CO ₂ ) reforming of methane over noble metal catalysts Pakhare, Devendra; Spivey, James Chem. Soc. Rev., Vol. 43, Issue 22 https://doi.org/10.1039/C3CS60395D	journal	January 2014
Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method Heyden, Andreas; Bell, Alexis T.; Keil, Frerich J. The Journal of Chemical Physics, Vol. 123, Issue 22 https://doi.org/10.1063/1.2104507	journal	December 2005
Robust and Coke-free Ni Catalyst Stabilized by 1–2 nm-Thick Multielement Oxide for Methane Dry Reforming He, Lei; Li, Mingrun; Li, Wen-Cui ACS Catalysis, Vol. 11, Issue 20 https://doi.org/10.1021/acscatal.1c02995	journal	September 2021
Engineering the oxygen vacancies enables Ni single-atom catalyst for stable and efficient C-H activation Wu, Jinwei; Gao, Jie; Lian, Shuangshuang Applied Catalysis B: Environmental, Vol. 314 https://doi.org/10.1016/j.apcatb.2022.121516	journal	October 2022
Dry reforming of methane on Ni-Fe-MgO catalysts: Influence of Fe on carbon-resistant property and kinetics Zhang, Tingting; Liu, Zhongxian; Zhu, Yi-An Applied Catalysis B: Environmental, Vol. 264 https://doi.org/10.1016/j.apcatb.2019.118497	journal	May 2020
High Alcohols Synthesis via Fischer–Tropsch Reaction at Cobalt Metal/Carbide Interface Pei, Yan-Peng; Liu, Jin-Xun; Zhao, Yong-Hui ACS Catalysis, Vol. 5, Issue 6 https://doi.org/10.1021/acscatal.5b00791	journal	May 2015

Similar Records

Steering the Methane Dry Reforming Reactivity of Ni/La₂O₃ Catalysts by Controlled In Situ Decomposition of Doped La₂NiO₄ Precursor Structures

Journal Article · 2020 · ACS Catalysis · OSTI ID:1810801

Bekheet, Maged F.; Delir Kheyrollahi Nezhad, Parastoo; Bonmassar, Nicolas; +13 more

Dry Reforming of Methane on Single-Site Ni/MgO Catalysts: Importance of Site Confinement

Journal Article · 2018 · ACS Catalysis · OSTI ID:1473658

Zuo, Zhijun; Liu, Shizhong; Wang, Zichun; +4 more

Design-controlled synthesis of IrO₂ sub-monolayers on Au nanoflowers: marrying plasmonic and electrocatalytic properties

Journal Article · 2020 · Nanoscale · OSTI ID:1676421

de Freitas, Isabel C.; Parreira, Luanna S.; Barbosa, Eduardo M.; +10 more

Related Subjects

36 MATERIALS SCIENCE

Title: Balancing elementary steps enables coke-free dry reforming of methane

Citation Formats

References (43)

Similar Records

Related Subjects