Controlling Selective C–O and C–H Bond Scission of Methanol by Supporting Pt on TiN and Mo2N Model Surfaces and Powder Catalysts

Yu, Marcus; Liao, Wenjie; Yuan, Yong; Zhou, Jiahua; Liu, Ping; Chen, Jingguang G.

doi:10.1021/acscatal.5c07156

Controlling Selective C–O and C–H Bond Scission of Methanol by Supporting Pt on TiN and Mo₂N Model Surfaces and Powder Catalysts

Journal Article · Sun Dec 07 00:00:00 EST 2025 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.5c07156· OSTI ID:3010080

Yu, Marcus ^[1]; ^[2]; ^[2]; Zhou, Jiahua ^[1]; ^[2]; ^[3]

Columbia Univ., New York, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Columbia Univ., New York, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Transition metal nitrides (TMNs) have been explored as effective supports for Pt due to their Pt-like electronic properties. However, there is a lack of fundamental understanding regarding the behavior of Pt on different TMNs (Pt/TMN). Herein two TMNs, Mo₂N and TiN, were modified with Pt and compared using methanol decomposition as a probe reaction via both ultrahigh vacuum (UHV) studies on thin films and ambient-pressure batch reactor studies of powder catalysts. Temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) measurements were conducted under UHV conditions with Mo₂N and TiN thin films. Mo₂N was shown to favor C–H bond scission to form CO with a 56.2% selectivity, while TiN favored C–O bond scission to form CH₄ with a 74.5% selectivity. The addition of 0.9 monolayers (MLs) of Pt increased C–H bond scission selectivity to 89.7% and 49.2% for Mo₂N and TiN respectively. Density functional theory (DFT) calculations on model surfaces revealed that the binding energy of O (BE_*O) was significantly reduced on Pt/TMNs, from −4.02 eV on Mo₂N to −1.31 eV on Pt/Mo₂N and −4.74 eV on TiN to −1.37 eV on Pt/TiN. As a result, C–O bond scission pathways were suppressed, leading to the preferential C–H bond scission that was observed experimentally. The C–O and C–H bond scission trends observed on thin films were then extended to powder catalysts, which demonstrated similar trends toward methanol decomposition. In conclusion, results from the current study establish that by combining UHV studies and DFT calculations over model surfaces, one can effectively predict the catalytic behavior of realistic TMN powder catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: AC02-05CH11231; SC0009476; SC0012653; SC0012704

OSTI ID:: 3010080

Report Number(s):: BNL--229251-2025-JAAM

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 24 Vol. 15; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (56)

Elastic Scattering Corrections in AES and XPS. II. Estimating Attenuation Lengths and Conditions Required for their Valid Use in Overlayer/Substrate Experiments Cumpson, P. J.; Seah, M. P. Surface and Interface Analysis, Vol. 25, Issue 6 https://doi.org/10.1002/(sici)1096-9918(199706)25:6<430::aid-sia254>3.3.co;2-z	journal	June 1997
Electro‐Catalytic Oxidation of Methanol Catalyzed by Facet‐Controlled Pt‐WC Nanoparticles on In Situ Synthesized Carbon Nanotubes Chu, You‐Qun; Peng, Rong‐Gui; Chen, Zhao‐Yang ChemElectroChem, Vol. 9, Issue 3 https://doi.org/10.1002/celc.202101370	journal	February 2022
Methanol as a Hydrogen Carrier: Kinetic and Thermodynamic Drivers for its CO ₂ ‐Based Synthesis and Reforming over Heterogeneous Catalysts Frei, Matthias S.; Mondelli, Cecilia; Short, Marion I. M. ChemSusChem https://doi.org/10.1002/cssc.202001518	journal	August 2020
Preparation and catalytic properties of transition metal carbides and nitrides Oyama, S. T. Catalysis Today, Vol. 15, Issue 2 https://doi.org/10.1016/0920-5861(92)80175-M	journal	June 1992
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Potential application of tungsten carbides as electrocatalysts III. Reactions of methanol, water, and hydrogen on Pt-modified C/W(111) surfaces Liu, N. Journal of Catalysis, Vol. 215, Issue 2 https://doi.org/10.1016/S0021-9517(03)00019-8	journal	April 2003
Reactions of methanol and water over carbide-modified Mo() Hwu, Henry H.; Chen, Jingguang G. Surface Science, Vol. 536, Issue 1-3 https://doi.org/10.1016/S0039-6028(03)00607-1	journal	June 2003
Adsorption of methanol, ethanol and water on well-characterized PtSn surface alloys Panja, Chameli; Saliba, Najat; Koel, Bruce E. Surface Science, Vol. 395, Issue 2-3 https://doi.org/10.1016/S0039-6028(97)00629-8	journal	January 1998
Cobalt-modified molybdenum carbide as a selective catalyst for hydrodeoxygenation of furfural Lin, Zhexi; Wan, Weiming; Yao, Siyu Applied Catalysis B: Environmental, Vol. 233 https://doi.org/10.1016/j.apcatb.2018.03.113	journal	October 2018
Machine learning prediction and experimental verification of Pt-modified nitride catalysts for ethanol reforming with reduced precious metal loading Denny, Steven R.; Lin, Zhexi; Porter, William N. Applied Catalysis B: Environmental, Vol. 312 https://doi.org/10.1016/j.apcatb.2022.121380	journal	September 2022
Using ethanol and isopropanol as biomass model compounds for understanding bond scission mechanisms over Cu/Mo2N catalysts Porter, William N.; Liao, Wenjie; Yu, Marcus Applied Catalysis B: Environment and Energy, Vol. 358 https://doi.org/10.1016/j.apcatb.2024.124362	journal	December 2024
Multilayer adsorption of methanol on platinum at low temperatures Selivanova, Aleksandra V.; Kremneva, Anna M.; Saraev, Andrey A. Applied Surface Science, Vol. 535 https://doi.org/10.1016/j.apsusc.2020.147717	journal	January 2021
Nanostructured transition metal nitrides for energy storage and fuel cells Dong, Shanmu; Chen, Xiao; Zhang, Xiaoying Coordination Chemistry Reviews, Vol. 257, Issue 13-14 https://doi.org/10.1016/j.ccr.2012.12.012	journal	July 2013
Trends in electrocatalytic activity and stability of transition-metal nitrides Mou, Hansen; Jeong, Jaehun Jason; Lamichhane, Bipin Chem Catalysis, Vol. 4, Issue 2 https://doi.org/10.1016/j.checat.2023.100867	journal	February 2024
Mo2N/C hybrid material as a promising support for the electro-oxidation of methanol and formic acid Cui, Zhiming; Yang, Minghui; DiSalvo, Francis J. Electrochemistry Communications, Vol. 33 https://doi.org/10.1016/j.elecom.2013.04.017	journal	August 2013
Direct methanol oxygen-ion conducting solid oxide fuel cell with an integrated in-situ cracking reactor Dang, Haochen; Song, Laizhen; Dong, Dehua Electrochimica Acta, Vol. 487 https://doi.org/10.1016/j.electacta.2024.144185	journal	May 2024
Boosting the activity and CO tolerance for methanol oxidation reaction in alkaline media by constructing the Pt-TMNs electrocatalysts Qi, Xiaoying; Ye, Na; Zhang, Riguang Fuel, Vol. 350 https://doi.org/10.1016/j.fuel.2023.128773	journal	October 2023
Large-scale stationary hydrogen storage via liquid organic hydrogen carriers Abdin, Zainul; Tang, Chunguang; Liu, Yun iScience, Vol. 24, Issue 9 https://doi.org/10.1016/j.isci.2021.102966	journal	September 2021
Correlating hydrogenation activity with binding energies of hydrogen and cyclohexene on M/Pt(111) (M = Fe, Co, Ni, Cu) bimetallic surfaces Humbert, M.; Chen, J. Journal of Catalysis, Vol. 257, Issue 2 https://doi.org/10.1016/j.jcat.2008.05.013	journal	July 2008
Theoretical prediction and experimental verification of low loading of platinum on titanium carbide as low-cost and stable electrocatalysts Kimmel, Yannick C.; Yang, Leerang; Kelly, Thomas G. Journal of Catalysis, Vol. 312 https://doi.org/10.1016/j.jcat.2014.02.002	journal	April 2014
Transition metal carbides and nitrides as catalysts for thermochemical reactions Lin, Zhexi; Denny, Steven R.; Chen, Jingguang G. Journal of Catalysis, Vol. 404 https://doi.org/10.1016/j.jcat.2021.06.022	journal	December 2021
Opportunities and Challenges in Utilizing Metal-Modified Transition Metal Carbides as Low-Cost Electrocatalysts Tackett, Brian M.; Sheng, Wenchao; Chen, Jingguang G. Joule, Vol. 1, Issue 2 https://doi.org/10.1016/j.joule.2017.07.002	journal	October 2017
Xe adsorption site distributions on Pt(111), Pt(221) and Pt(531) Gellman, Andrew J.; Baker, L.; Holsclaw, B. S. Surface Science, Vol. 646 https://doi.org/10.1016/j.susc.2015.10.062	journal	April 2016
Recent Advances in Carbon Dioxide Hydrogenation to Methanol via Heterogeneous Catalysis Jiang, Xiao; Nie, Xiaowa; Guo, Xinwen Chemical Reviews, Vol. 120, Issue 15 https://doi.org/10.1021/acs.chemrev.9b00723	journal	February 2020
Steam Reforming of Methanol for Hydrogen Production: A Critical Analysis of Catalysis, Processes, and Scope Ranjekar, Apoorva M.; Yadav, Ganapati D. Industrial & Engineering Chemistry Research, Vol. 60, Issue 1 https://doi.org/10.1021/acs.iecr.0c05041	journal	January 2021
Synergistic and Durable Pt-WC Catalyst for Methanol Electro-Oxidation in Ionic Liquid Aqueous Solution Zhou, Yang; Li, Xiaolin; Yu, Changlin ACS Applied Energy Materials, Vol. 2, Issue 12 https://doi.org/10.1021/acsaem.9b01332	journal	December 2019
Correlating Experimentally Determined Hydrogen Binding Energy with Hydrogen Evolution Activity over Metal Monolayers on Molybdenum Nitride Turaczy, Kevin K.; Liao, Wenjie; Mou, Hansen ACS Catalysis, Vol. 13, Issue 21 https://doi.org/10.1021/acscatal.3c04063	journal	October 2023
Controlling Bond Scission Pathways of Isopropanol on Fe- and Pt-Modified Mo₂N Model Surfaces and Powder Catalysts Porter, William N.; Mera, Hilda A.; Liao, Wenjie ACS Catalysis, Vol. 14, Issue 3 https://doi.org/10.1021/acscatal.3c04700	journal	January 2024
Power Generation by Flat-Tube Solid Oxide Fuel Cells with Enhanced Internal Reforming of Methanol Sang, Junkang; Li, Yuqing; Yang, Jun ACS Sustainable Chemistry & Engineering, Vol. 10, Issue 19 https://doi.org/10.1021/acssuschemeng.2c00518	journal	May 2022
Methanol Steam Reforming for Hydrogen Production Palo, Daniel R.; Dagle, Robert A.; Holladay, Jamie D. Chemical Reviews, Vol. 107, Issue 10 https://doi.org/10.1021/cr050198b	journal	October 2007
Carbide and Nitride Overlayers on Early Transition Metal Surfaces: Preparation, Characterization, and Reactivities Chen, Jingguang G. Chemical Reviews, Vol. 96, Issue 4 https://doi.org/10.1021/cr950232u	journal	January 1996
Trends in the Hydrogen Evolution Activity of Metal Carbide Catalysts Michalsky, Ronald; Zhang, Yin-Jia; Peterson, Andrew A. ACS Catalysis, Vol. 4, Issue 5 https://doi.org/10.1021/cs500056u	journal	March 2014
A New Class of Electrocatalysts for Hydrogen Production from Water Electrolysis: Metal Monolayers Supported on Low-Cost Transition Metal Carbides Esposito, Daniel V.; Hunt, Sean T.; Kimmel, Yannick C. Journal of the American Chemical Society, Vol. 134, Issue 6 https://doi.org/10.1021/ja208656v	journal	February 2012
Reaction of Ethylene with Clean and Carbide-Modified Mo(110): Converting Surface Reactivities of Molybdenum to Pt-Group Metals Frühberger, B.; Chen, J. G. Journal of the American Chemical Society, Vol. 118, Issue 46 https://doi.org/10.1021/ja960656l	journal	January 1996
Unraveling Unique Surface Chemistry of Transition Metal Nitrides in Controlling Selective C–O Bond Scission Pathways of Glycerol Lin, Zhexi; Ammal, Salai C.; Denny, Steven R. JACS Au, Vol. 2, Issue 2 https://doi.org/10.1021/jacsau.1c00403	journal	January 2022
Potential Application of Tungsten Carbides as Electrocatalysts. 1. Decomposition of Methanol over Carbide-Modified W(111) Hwu, Henry H.; Chen, Jingguang G.; Kourtakis, Kostantinos The Journal of Physical Chemistry B, Vol. 105, Issue 41 https://doi.org/10.1021/jp0116196	journal	October 2001
Potential Application of Tungsten Carbides as Electrocatalysts. 2. Coadsorption of CO and H ₂ O on Carbide-Modified W(111) Hwu, Henry H.; Polizzotti, Brian D.; Chen, Jingguang G. The Journal of Physical Chemistry B, Vol. 105, Issue 41 https://doi.org/10.1021/jp0116205	journal	October 2001
Potential Application of Tungsten Carbides as Electrocatalysts: 4. Reactions of Methanol, Water, and Carbon Monoxide over Carbide-Modified W(110) Hwu, Henry H.; Chen, Jingguang G. The Journal of Physical Chemistry B, Vol. 107, Issue 9 https://doi.org/10.1021/jp0269118	journal	March 2003
Brønsted−Evans−Polanyi Relation of Multistep Reactions and Volcano Curve in Heterogeneous Catalysis Cheng, Jun; Hu, P.; Ellis, Peter The Journal of Physical Chemistry C, Vol. 112, Issue 5 https://doi.org/10.1021/jp711191j	journal	February 2008
Quantification of Active Sites for the Determination of Methanol Oxidation Turn-over Frequencies Using Methanol Chemisorption and in Situ Infrared Techniques. 1. Supported Metal Oxide Catalysts Burcham, Loyd J.; Briand, Laura E.; Wachs, Israel E. Langmuir, Vol. 17, Issue 20 https://doi.org/10.1021/la010009u	journal	October 2001
Net reduction of CO2 via its thermocatalytic and electrocatalytic transformation reactions in standard and hybrid processes Tackett, Brian M.; Gomez, Elaine; Chen, Jingguang G. Nature Catalysis, Vol. 2, Issue 5 https://doi.org/10.1038/s41929-019-0266-y	journal	April 2019
Enhanced Electrocatalytic Performance for Oxygen Reduction via Active Interfaces of Layer-By-Layered Titanium Nitride/Titanium Carbonitride Structures Jin, Zhaoyu; Li, Panpan; Xiao, Dan Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep06712	journal	October 2014
Mesoporous titanium nitride supported Pt nanoparticles as high performance catalysts for methanol electrooxidation Yang, Minghui; Cui, Zhiming; DiSalvo, Francis J. Phys. Chem. Chem. Phys., Vol. 15, Issue 4 https://doi.org/10.1039/C2CP44215A	journal	January 2013
Density functional theory studies of transition metal carbides and nitrides as electrocatalysts Tian, Dong; Denny, Steven R.; Li, Kongzhai Chemical Society Reviews, Vol. 50, Issue 22 https://doi.org/10.1039/D1CS00590A	journal	January 2021
Pt- and Pd-modified transition metal nitride catalysts for the hydrogen evolution reaction Ologunagba, Damilola; Kattel, Shyam Physical Chemistry Chemical Physics, Vol. 24, Issue 20 https://doi.org/10.1039/D2CP00792D	journal	January 2022
Recent progress in the synthesis of transition metal nitride catalysts and their applications in electrocatalysis Yang, Zheng-Gang; Xu, Hui-Min; Shuai, Ting-Yu Nanoscale, Vol. 15, Issue 28 https://doi.org/10.1039/D3NR01607B	journal	January 2023
Transition metal nitride catalysts for selective conversion of oxygen-containing molecules Porter, William N.; Turaczy, Kevin K.; Yu, Marcus Chemical Science, Vol. 15, Issue 18 https://doi.org/10.1039/D4SC01314J	journal	January 2024
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
The atomic simulation environment—a Python library for working with atoms Hjorth Larsen, Ask; Jørgen Mortensen, Jens; Blomqvist, Jakob Journal of Physics: Condensed Matter, Vol. 29, Issue 27 https://doi.org/10.1088/1361-648X/aa680e	journal	June 2017
Ab initio molecular dynamics for open-shell transition metals Kresse, G.; Hafner, J. Physical Review B, Vol. 48, Issue 17 https://doi.org/10.1103/PhysRevB.48.13115	journal	November 1993
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
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
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
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
Platinum-Like Behavior of Tungsten Carbide in Surface Catalysis Levy, R. B.; Boudart, M. Science, Vol. 181, Issue 4099 https://doi.org/10.1126/science.181.4099.547	journal	August 1973
Transition Metal Nitrides for Electrocatalytic Application: Progress and Rational Design Meng, Zihan; Zheng, Shuhong; Luo, Ren Nanomaterials, Vol. 12, Issue 15 https://doi.org/10.3390/nano12152660	journal	August 2022

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Controlling Selective C–O and C–H Bond Scission of Methanol by Supporting Pt on TiN and Mo2N Model Surfaces and Powder Catalysts

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Controlling Selective C–O and C–H Bond Scission of Methanol by Supporting Pt on TiN and Mo₂N Model Surfaces and Powder Catalysts