Reversible dehydrogenation and rehydrogenation of cyclohexane and methylcyclohexane by single-site platinum catalyst

Chen, Luning; Verma, Pragya; Hou, Kaipeng; Qi, Zhiyuan; Zhang, Shuchen; Liu, Yi-Sheng; Guo, Jinghua; Stavila, Vitalie; Allendorf, Mark D.; Zheng, Lansun; Salmeron, Miquel; Prendergast, David; Somorjai, Gabor A.; Su, Ji

doi:10.1038/s41467-022-28607-y

Reversible dehydrogenation and rehydrogenation of cyclohexane and methylcyclohexane by single-site platinum catalyst

Journal Article · Tue Mar 01 00:00:00 EST 2022 · Nature Communications

DOI:https://doi.org/10.1038/s41467-022-28607-y· OSTI ID:1846846

Chen, Luning; Verma, Pragya; Hou, Kaipeng; Qi, Zhiyuan; Zhang, Shuchen; ; ; ; ; Zheng, Lansun; ; ; ;

Abstract

Developing highly efficient and reversible hydrogenation-dehydrogenation catalysts shows great promise for hydrogen storage technologies with highly desirable economic and ecological benefits. Herein, we show that reaction sites consisting of single Pt atoms and neighboring oxygen vacancies (V _O ) can be prepared on CeO ₂ (Pt ₁ /CeO ₂ ) with unique catalytic properties for the reversible dehydrogenation and rehydrogenation of large molecules such as cyclohexane and methylcyclohexane. Specifically, we find that the dehydrogenation rate of cyclohexane and methylcyclohexane on such sites can reach values above 32,000 mol _H2 mol _Pt ⁻¹ h ⁻¹ , which is 309 times higher than that of conventional supported Pt nanoparticles. Combining of DRIFTS, AP-XPS, EXAFS, and DFT calculations, we show that the Pt ₁ /CeO ₂ catalyst exhibits a super-synergistic effect between the catalytic Pt atom and its support, involving redox coupling between Pt and Ce ions, enabling adsorption, activation and reaction of large molecules with sufficient versatility to drive abstraction/addition of hydrogen without requiring multiple reaction sites.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; NA0003525

OSTI ID:: 1846846

Alternate ID(s):: OSTI ID: 1885464

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 13; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

References (58)

Asymmetric Oxygen Vacancies: the Intrinsic Redox Active Sites in Metal Oxide Catalysts Yu, Kai; Lou, Lan‐Lan; Liu, Shuangxi Advanced Science, Vol. 7, Issue 2 https://doi.org/10.1002/advs.201901970	journal	November 2019
Maximizing the Number of Interfacial Sites in Single-Atom Catalysts for the Highly Selective, Solvent-Free Oxidation of Primary Alcohols Li, Tianbo; Liu, Fei; Tang, Yan Angewandte Chemie International Edition, Vol. 57, Issue 26 https://doi.org/10.1002/anie.201803272	journal	May 2018
Ce 3d XPS investigation of cerium oxides and mixed cerium oxide (CexTiyOz) Bêche, Eric; Charvin, Patrice; Perarnau, Danielle Surface and Interface Analysis, Vol. 40, Issue 3-4 https://doi.org/10.1002/sia.2686	journal	January 2008
The Equilibrium Constant for the Methylcyclohexane–Toluene System Schildhauer, T.; Newson, E.; Müller, St Journal of Catalysis, Vol. 198, Issue 2 https://doi.org/10.1006/jcat.2000.3133	journal	March 2001
The dehydrogenation and hydrogenolysis of cyclohexane and cyclohexene on stepped (high miller index) platinum surfaces Blakely, D. Journal of Catalysis, Vol. 42, Issue 2 https://doi.org/10.1016/0021-9517(76)90252-9	journal	February 1976
The infrared spectrum of cyclohexane adsorbed on Pt(111) Chesters, M. A.; Gardner, P. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 46, Issue 6 https://doi.org/10.1016/0584-8539(90)80018-T	journal	January 1990
Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces Mullins, D. R.; Overbury, S. H.; Huntley, D. R. Surface Science, Vol. 409, Issue 2 https://doi.org/10.1016/S0039-6028(98)00257-X	journal	July 1998
Study of CeO2 XPS spectra by factor analysis: reduction of CeO2 Holgado, Juan P.; Alvarez, Rafael; Munuera, Guillermo Applied Surface Science, Vol. 161, Issue 3-4 https://doi.org/10.1016/S0169-4332(99)00577-2	journal	July 2000
Efficient hydrogen production using cyclohexane and decalin by pulse-spray mode reactor with Pt catalysts Kariya, Nobuko; Fukuoka, Atsushi; Utagawa, Tadashi Applied Catalysis A: General, Vol. 247, Issue 2 https://doi.org/10.1016/S0926-860X(03)00104-2	journal	July 2003
Stabilizing platinum atoms on CeO2 oxygen vacancies by metal-support interaction induced interface distortion: Mechanism and application Jiang, Zeyu; Jing, Meizan; Feng, Xiangbo Applied Catalysis B: Environmental, Vol. 278 https://doi.org/10.1016/j.apcatb.2020.119304	journal	December 2020
XPS study of ion irradiated and unirradiated CeO2 bulk and thin film samples Maslakov, Konstantin I.; Teterin, Yury A.; Popel, Aleksej J. Applied Surface Science, Vol. 448 https://doi.org/10.1016/j.apsusc.2018.04.077	journal	August 2018
A hydrogen economy: opportunities and challenges Tseng, Phillip; Lee, John; Friley, Paul Energy, Vol. 30, Issue 14 https://doi.org/10.1016/j.energy.2004.07.015	journal	November 2005
Development of dehydrogenation catalyst for hydrogen generation in organic chemical hydride method Okada, Y.; Sasaki, E.; Watanabe, E. International Journal of Hydrogen Energy, Vol. 31, Issue 10 https://doi.org/10.1016/j.ijhydene.2005.11.014	journal	August 2006
Single-Atom Catalysts: Synthetic Strategies and Electrochemical Applications Chen, Yuanjun; Ji, Shufang; Chen, Chen Joule, Vol. 2, Issue 7 https://doi.org/10.1016/j.joule.2018.06.019	journal	July 2018
Single atom is not alone: Metal–support interactions in single-atom catalysis Qi, Kun; Chhowalla, Manish; Voiry, Damien Materials Today, Vol. 40 https://doi.org/10.1016/j.mattod.2020.07.002	journal	November 2020
Dehydrogenation of methylcyclohexane to toluene over partially reduced silica-supported Pt-Mo catalysts Boufaden, N.; Akkari, R.; Pawelec, B. Journal of Molecular Catalysis A: Chemical, Vol. 420 https://doi.org/10.1016/j.molcata.2016.04.011	journal	August 2016
Development of Pt/TiO2 nanohybrids-modified SWCNT electrode for sensitive hydrogen peroxide detection Han, Kwi Nam; Li, Cheng Ai; Bui, Minh-Phuong Ngoc Sensors and Actuators B: Chemical, Vol. 174 https://doi.org/10.1016/j.snb.2012.08.066	journal	November 2012
Liquid Organic Hydrogen Carriers (LOHCs): Toward a Hydrogen-free Hydrogen Economy Preuster, Patrick; Papp, Christian; Wasserscheid, Peter Accounts of Chemical Research, Vol. 50, Issue 1 https://doi.org/10.1021/acs.accounts.6b00474	journal	December 2016
Surface and Interface Control in Nanoparticle Catalysis Xie, Chenlu; Niu, Zhiqiang; Kim, Dohyung Chemical Reviews, Vol. 120, Issue 2 https://doi.org/10.1021/acs.chemrev.9b00220	journal	October 2019
The Prospect of Hydrogen Storage Using Liquid Organic Hydrogen Carriers Modisha, Phillimon M.; Ouma, Cecil N. M.; Garidzirai, Rudaviro Energy & Fuels, Vol. 33, Issue 4 https://doi.org/10.1021/acs.energyfuels.9b00296	journal	March 2019
Active, Selective, and Durable Catalyst for Alkane Dehydrogenation Based on a Well-Designed Trimetallic Alloy Nakaya, Yuki; Miyazaki, Masayoshi; Yamazoe, Seiji ACS Catalysis, Vol. 10, Issue 9 https://doi.org/10.1021/acscatal.0c00151	journal	April 2020
Highly-Dispersed Zinc Species on Zeolites for the Continuous and Selective Dehydrogenation of Ethane with CO ₂ as a Soft Oxidant Liu, Jiaxu; He, Ning; Zhang, Zhenmei ACS Catalysis, Vol. 11, Issue 5 https://doi.org/10.1021/acscatal.1c00126	journal	February 2021
Surface Engineering Protocol To Obtain an Atomically Dispersed Pt/CeO ₂ Catalyst with High Activity and Stability for CO Oxidation Chen, Jiayu; Wanyan, Yongjin; Zeng, Jianxin ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 11 https://doi.org/10.1021/acssuschemeng.8b02613	journal	September 2018
Strong metal-support interactions Tauster, S. J. Accounts of Chemical Research, Vol. 20, Issue 11 https://doi.org/10.1021/ar00143a001	journal	November 1987
Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao Accounts of Chemical Research, Vol. 46, Issue 8 https://doi.org/10.1021/ar300361m	journal	April 2013
Spillover in Heterogeneous Catalysis Conner, W. Curtis.; Falconer, John L. Chemical Reviews, Vol. 95, Issue 3 https://doi.org/10.1021/cr00035a014	journal	May 1995
Recent Developments in the Synthesis of Supported Catalysts Munnik, Peter; de Jongh, Petra E.; de Jong, Krijn P. Chemical Reviews, Vol. 115, Issue 14 https://doi.org/10.1021/cr500486u	journal	June 2015
Pure Hydrogen Production by Partial Dehydrogenation of Cyclohexane and Methylcyclohexane over Nanotube-Supported Pt and Pd Catalysts Wang, Yuguo; Shah, Naresh; Huffman, Gerald P. Energy & Fuels, Vol. 18, Issue 5 https://doi.org/10.1021/ef049959o	journal	September 2004
Fully Dispersed Rh Ensemble Catalyst To Enhance Low-Temperature Activity Jeong, Hojin; Lee, Geonhee; Kim, Beom-Sik Journal of the American Chemical Society, Vol. 140, Issue 30 https://doi.org/10.1021/jacs.8b04613	journal	July 2018
Uniformity Is Key in Defining Structure–Function Relationships for Atomically Dispersed Metal Catalysts: The Case of Pt/CeO ₂ Resasco, Joaquin; DeRita, Leo; Dai, Sheng Journal of the American Chemical Society, Vol. 142, Issue 1 https://doi.org/10.1021/jacs.9b09156	journal	December 2019
Efficient Hydrogen Production from Methanol Using a Single-Site Pt ₁ /CeO ₂ Catalyst Chen, Lu-Ning; Hou, Kai-Peng; Liu, Yi-Sheng Journal of the American Chemical Society, Vol. 141, Issue 45 https://doi.org/10.1021/jacs.9b09431	journal	October 2019
Genesis and Evolution of Surface Species during Pt Atomic Layer Deposition on Oxide Supports Characterized by in Situ XAFS Analysis and Water−Gas Shift Reaction Setthapun, Worajit; Williams, W. Damion; Kim, Seung Min The Journal of Physical Chemistry C, Vol. 114, Issue 21 https://doi.org/10.1021/jp911178m	journal	May 2010
Platinum Nanoparticle Shape Effects on Benzene Hydrogenation Selectivity Bratlie, Kaitlin M.; Lee, Hyunjoo; Komvopoulos, Kyriakos Nano Letters, Vol. 7, Issue 10 https://doi.org/10.1021/nl0716000	journal	October 2007
Materials for fuel-cell technologies Steele, Brian C. H.; Heinzel, Angelika Nature, Vol. 414, Issue 6861, p. 345-352 https://doi.org/10.1038/35104620	journal	November 2001
Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide Nielsen, Martin; Alberico, Elisabetta; Baumann, Wolfgang Nature, Vol. 495, Issue 7439 https://doi.org/10.1038/nature11891	journal	February 2013
Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts Shan, Junjun; Li, Mengwei; Allard, Lawrence F. Nature, Vol. 551, Issue 7682 https://doi.org/10.1038/nature24640	journal	November 2017
Single-atom catalysis of CO oxidation using Pt1/FeOx Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng Nature Chemistry, Vol. 3, Issue 8 https://doi.org/10.1038/nchem.1095	journal	July 2011
A new and selective cycle for dehydrogenation of linear and cyclic alkanes under mild conditions using a base metal Solowey, Douglas P.; Mane, Manoj V.; Kurogi, Takashi Nature Chemistry, Vol. 9, Issue 11 https://doi.org/10.1038/nchem.2795	journal	June 2017
In situ click chemistry generation of cyclooxygenase-2 inhibitors Bhardwaj, Atul; Kaur, Jatinder; Wuest, Melinda Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-016-0009-6	journal	February 2017
Structural absorption by barbule microstructures of super black bird of paradise feathers McCoy, Dakota E.; Feo, Teresa; Harvey, Todd Alan Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-017-02088-w	journal	January 2018
Heterogeneous single-atom catalysis Wang, Aiqin; Li, Jun; Zhang, Tao Nature Reviews Chemistry, Vol. 2, Issue 6 https://doi.org/10.1038/s41570-018-0010-1	journal	May 2018
Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity van Deelen, Tom W.; Hernández Mejía, Carlos; de Jong, Krijn P. Nature Catalysis, Vol. 2, Issue 11 https://doi.org/10.1038/s41929-019-0364-x	journal	November 2019
Highly durable metal ensemble catalysts with full dispersion for automotive applications beyond single-atom catalysts Jeong, Hojin; Kwon, Ohmin; Kim, Beom-Sik Nature Catalysis, Vol. 3, Issue 4 https://doi.org/10.1038/s41929-020-0427-z	journal	February 2020
Quantitative depth profiling of Ce ³⁺ in Pt/CeO ₂ by in situ high-energy XPS in a hydrogen atmosphere Kato, Shunsuke; Ammann, Markus; Huthwelker, Thomas Physical Chemistry Chemical Physics, Vol. 17, Issue 7 https://doi.org/10.1039/C4CP05643D	journal	January 2015
Environmental and health impact assessment of Liquid Organic Hydrogen Carrier (LOHC) systems – challenges and preliminary results Markiewicz, M.; Zhang, Y. Q.; Bösmann, A. Energy & Environmental Science, Vol. 8, Issue 3 https://doi.org/10.1039/C4EE03528C	journal	January 2015
Selective loading of platinum or silver cocatalyst onto a hydrogen-evolution photocatalyst in a silver-mediated all solid-state Z-scheme system for enhanced overall water splitting Osaki, Junya; Yoda, Masaomi; Takashima, Toshihiro RSC Advances, Vol. 9, Issue 71 https://doi.org/10.1039/C9RA09421K	journal	January 2019
Silica-supported, narrowly distributed, subnanometric Pt–Zn particles from single sites with high propane dehydrogenation performance Rochlitz, Lukas; Searles, Keith; Alfke, Jan Chemical Science, Vol. 11, Issue 6 https://doi.org/10.1039/C9SC05599A	journal	January 2020
Recent progress in heterogeneous metal and metal oxide catalysts for direct dehydrogenation of ethane and propane Dai, Yihu; Gao, Xing; Wang, Qiaojuan Chemical Society Reviews, Vol. 50, Issue 9 https://doi.org/10.1039/D0CS01260B	journal	January 2021
A future energy supply based on Liquid Organic Hydrogen Carriers (LOHC) Teichmann, Daniel; Arlt, Wolfgang; Wasserscheid, Peter Energy & Environmental Science, Vol. 4, Issue 8 https://doi.org/10.1039/c1ee01454d	journal	January 2011
Synergistic catalysis: A powerful synthetic strategy for new reaction development Allen, Anna E.; MacMillan, David W. C. Chemical Science, Vol. 3, Issue 3 https://doi.org/10.1039/c2sc00907b	journal	January 2012
Theoretical understanding of the stability of single-atom catalysts Liu, Jin-Cheng; Tang, Yan; Wang, Yang-Gang National Science Review, Vol. 5, Issue 5 https://doi.org/10.1093/nsr/nwy094	journal	September 2018
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
Potential Environmental Impact of a Hydrogen Economy on the Stratosphere Tromp, T. K. Science, Vol. 300, Issue 5626 https://doi.org/10.1126/science.1085169	journal	June 2003
Air Pollution and Climate-Forcing Impacts of a Global Hydrogen Economy Schultz, M. G. Science, Vol. 302, Issue 5645 https://doi.org/10.1126/science.1089527	journal	October 2003
Photochemical route for synthesizing atomically dispersed palladium catalysts Liu, P.; Zhao, Y.; Qin, R. Science, Vol. 352, Issue 6287 https://doi.org/10.1126/science.aaf5251	journal	May 2016
Thermally stable single-atom platinum-on-ceria catalysts via atom trapping Jones, J.; Xiong, H.; DeLaRiva, A. T. Science, Vol. 353, Issue 6295 https://doi.org/10.1126/science.aaf8800	journal	July 2016
Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water-gas shift reaction Yao, Siyu; Zhang, Xiao; Zhou, Wu Science, Vol. 357, Issue 6349 https://doi.org/10.1126/science.aah4321	journal	June 2017
Activation of surface lattice oxygen in single-atom Pt/CeO ₂ for low-temperature CO oxidation Nie, Lei; Mei, Donghai; Xiong, Haifeng Science, Vol. 358, Issue 6369 https://doi.org/10.1126/science.aao2109	journal	December 2017

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