Reaction pathways for HCN on transition metal surfaces

Abdel-Rahman, Mohammed; Feng, Xu; Muir, Mark; Ghale, Kushal; Xu, Ye; Trenary, Michael

doi:10.1039/c8cp07548d

Reaction pathways for HCN on transition metal surfaces

Journal Article · Mon Feb 18 00:00:00 EST 2019 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c8cp07548d· OSTI ID:1530582

Abdel-Rahman, Mohammed ^[1]; ^[2]; Muir, Mark ^[1]; Ghale, Kushal ^[3]; ^[3]; ^[1]

Univ. of Illinois, Chicago, IL (United States)
Univ. of Illinois, Chicago, IL (United States)SA
Louisiana State Univ., Baton Rouge, LA (United States)

In this work, the adsorption and decomposition of HCN on the Pd(111) and Ru(001) surfaces have been studied with reflection absorption infrared spectroscopy and density functional theory calculations. The results are compared to earlier studies of HCN adsorption on the Pt(111) and Cu(100) surfaces. In all cases the initial adsorption at low temperatures gives rise to a ν(C–H) stretch peak at ~3300 cm^–1, which is very close to the gas phase value indicating that the triple CN bond is retained for the adsorbed molecule. When the Pd(111) surface is heated to room temperature, the HCN is converted to the aminocarbyne species, CNH₂, which was also observed on the Pt(111) surface. DFT calculations confirm the high stability of CNH₂ on Pd(111), and suggest a bi-molecular mechanism for its formation. When HCN on Cu(100) is heated, it desorbs without reaction. In contrast, no stable intermediates are detected on Ru(001) as the surface is heated, indicating that HCN decomposes completely to atomic species.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: Donors of the American Chemical Society Petroleum Research Fund; National Science Foundation (NSF); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1530582

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 9 Vol. 21; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

The infrared spectra of HCN isotopes in argon matrices Pacansky, Jacob; Calder, G. Vincent Journal of Molecular Structure, Vol. 14, Issue 3 https://doi.org/10.1016/0022-2860(72)85185-8	journal	December 1972
The hydrogenation of CN on Pd(111) and Pd(100) Kordesch, M. E.; Stenzel, W.; Conrad, H. Surface Science, Vol. 175, Issue 1 https://doi.org/10.1016/0039-6028(86)90075-0	journal	September 1986
Effect of surface temperature on the sorption of hydrogen by Pd(111) Gdowski, G. E.; Felter, T. E.; Stulen, R. H. Surface Science, Vol. 181, Issue 3 https://doi.org/10.1016/0039-6028(87)90187-7	journal	March 1987
A comparison of single-, double-, triple-bonded and aromatic CN compounds on Pd(111) and (100) Kordesch, M. E.; Stenzel, W.; Conrad, H. Surface Science, Vol. 205, Issue 1-2 https://doi.org/10.1016/0039-6028(88)90166-5	journal	October 1988
An angle-resolved photoemission investigation of CN, HCN and C2N2 adsorbed on Pd{111} using synchrotron radiation Somers, J. S.; Kordesch, M. E.; Hemmen, R. Surface Science, Vol. 198, Issue 3 https://doi.org/10.1016/0039-6028(88)90374-3	journal	January 1988
Dissociative adsorption of hydrogen on Cu(100) at low temperatures Rasmussen, P. B.; Holmblad, P. M.; Christoffersen, H. Surface Science, Vol. 287-288 https://doi.org/10.1016/0039-6028(93)90746-7	journal	May 1993
Formation of aminomethylidyne from hydrogen cyanide on Pt(111) Jentz, D.; Celio, H.; Mills, P. Surface Science, Vol. 341, Issue 1-2 https://doi.org/10.1016/0039-6028(95)00601-X	journal	November 1995
Effect of surface temperature on the sorption of hydrogen by Pd(111) Gdowski, G. E.; Felter, T. E.; Stulen, R. H. Surface Science Letters, Vol. 181, Issue 3 https://doi.org/10.1016/0167-2584(87)90365-3	journal	March 1987
A comparison of single-, double-, triple-bonded and aromatic CN compounds on Pd(111) and (100) I. HREELS of NCCN, ethylenediamine and s-triazine Kordesch, M. E.; Stenzel, W.; Conrad, H. Surface Science Letters, Vol. 186, Issue 1-2 https://doi.org/10.1016/0167-2584(87)90647-5	journal	July 1987
A comparison of single-, double-, triple-bonded and aromatic CN compounds on Pd(111) and (100) I. HREELS of NCCN, ethylenediamine and s-triazine Kordesch, M. E.; Stenzel, W.; Conrad, H. Surface Science Letters, Vol. 186, Issue 3 https://doi.org/10.1016/0167-2584(87)91293-x	journal	August 1987
Dissociative adsorption of hydrogen on Cu(100) at low temperatures Rasmussen, P. B.; Holmblad, P. M.; Christoffersen, H. Surface Science Letters, Vol. 287-288 https://doi.org/10.1016/0167-2584(93)90395-y	journal	May 1993
A comparison of single-, double-, triple-bonded and aromatic CN compounds on Pd(111) and (100) I. Hreels of NCCN, ethylenediamine and s-triazine Kordesch, M. E.; Stenzel, W.; Conrad, H. Surface Science, Vol. 186, Issue 3 https://doi.org/10.1016/S0039-6028(87)80396-5	journal	August 1987
The surface chemistry of CN and H on Pt(111) Jentz, D.; Mills, P.; Celio, H. Surface Science, Vol. 368, Issue 1-3 https://doi.org/10.1016/S0039-6028(96)01075-8	journal	December 1996
The surface chemistry of the CN group: geometry and bonding Kordesch, M. E.; Lindner, Th.; Somers, J. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 43, Issue 12 https://doi.org/10.1016/S0584-8539(87)80048-X	journal	January 1987
Ultraviolet photolysis and proton irradiation of astrophysical ice analogs containing hydrogen cyanide Gerakines, P. A.; Moore, M. H.; Hudson, R. L. Icarus, Vol. 170, Issue 1 https://doi.org/10.1016/j.icarus.2004.02.005	journal	July 2004
Atomic and molecular adsorption on Pt(111) Ford, Denise C.; Xu, Ye; Mavrikakis, Manos Surface Science, Vol. 587, Issue 3 https://doi.org/10.1016/j.susc.2005.04.028	journal	August 2005
Atomic and molecular adsorption on Pd(111) Herron, Jeffrey A.; Tonelli, Scott; Mavrikakis, Manos Surface Science, Vol. 606, Issue 21-22 https://doi.org/10.1016/j.susc.2012.07.003	journal	November 2012
A benchmark database for adsorption bond energies to transition metal surfaces and comparison to selected DFT functionals Wellendorff, Jess; Silbaugh, Trent L.; Garcia-Pintos, Delfina Surface Science, Vol. 640 https://doi.org/10.1016/j.susc.2015.03.023	journal	October 2015
Deposition and characterization of stoichiometric films of V 2 O 5 on Pd(111) Feng, Xu; Abdel-Rahman, Mohammed K.; Kruppe, Christopher M. Surface Science, Vol. 664 https://doi.org/10.1016/j.susc.2017.05.004	journal	October 2017
DFT-Based Method for More Accurate Adsorption Energies: An Adaptive Sum of Energies from RPBE and vdW Density Functionals Hensley, Alyssa J. R.; Ghale, Kushal; Rieg, Carolin The Journal of Physical Chemistry C, Vol. 121, Issue 9 https://doi.org/10.1021/acs.jpcc.6b10187	journal	February 2017
Scanning kinetic spectroscopy and temperature-programmed desorption studies of the adsorption and decomposition of hydrogen cyanide on the nickel(111) surface Hagans, P. L.; Chorkendorff, I.; Yates, J. T. The Journal of Physical Chemistry, Vol. 92, Issue 2 https://doi.org/10.1021/j100313a045	journal	January 1988
Matrix infrared spectra of the ammonia-hydrogen cyanide and ammonia-hydrogen cyanide (1:2) complexes in solid argon Bohn, Robert B.; Andrews, Lester The Journal of Physical Chemistry, Vol. 93, Issue 10 https://doi.org/10.1021/j100347a022	journal	May 1989
Hydrogen cyanide adsorption on the palladium(111) surface: surface temperature and coverage dependence Guo, X.; Hoffman, A.; Yates, J. T. The Journal of Physical Chemistry, Vol. 93, Issue 10 https://doi.org/10.1021/j100347a068	journal	May 1989
Formation of Iminium (CNH ₂ ) Species from Cyanogen (C ₂ N ₂ ) and Hydrogen on Pt(111) Mills, P.; Jentz, D.; Trenary, M. Journal of the American Chemical Society, Vol. 119, Issue 38 https://doi.org/10.1021/ja9706110	journal	September 1997
Mechanistic Switch between Oxidative (Andrussow) and Nonoxidative (Degussa) Formation of HCN on Pt(111) by Density Functional Theory Gómez-Díaz, Jaime; López, Núria The Journal of Physical Chemistry C, Vol. 115, Issue 13 https://doi.org/10.1021/jp1093349	journal	March 2011
Kinetics of HCN Decomposition on the Pt(111) Surface by Time-Dependent Infrared Spectroscopy Hu, Xiaofeng; Trenary, Michael The Journal of Physical Chemistry C, Vol. 116, Issue 6 https://doi.org/10.1021/jp209491q	journal	February 2012
Kinetics of Aminocarbyne Formation on Pt(111) Hu, Xiaofeng; Yin, Jun; Meyer, Randall J. The Journal of Physical Chemistry C, Vol. 119, Issue 26 https://doi.org/10.1021/jp507026k	journal	September 2014
Control of Reaction Selectivity via Surface Oxygen Coverage: Thermal Decomposition of Azomethane on Rh(111) Bol, C. W. J.; Kovacs, J. D.; Chen, M. The Journal of Physical Chemistry B, Vol. 101, Issue 33 https://doi.org/10.1021/jp962681j	journal	August 1997
Observation of Tunneling in the Hydrogenation of Atomic Nitrogen on the Ru(001) Surface to Form NH Waluyo, Iradwikanari; Ren, Yuan; Trenary, Michael The Journal of Physical Chemistry Letters, Vol. 4, Issue 21 https://doi.org/10.1021/jz4020585	journal	October 2013
Molecular Adsorption of HCN on Pt(111) and Cu(100) Celio, H.; Mills, P.; Jentz, D. Langmuir, Vol. 14, Issue 6 https://doi.org/10.1021/la970734y	journal	March 1998
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets Chen, Ruyi; Cui, Qirui; Liao, Liyang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23414-3	journal	May 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-58835-5	journal	February 2020
Thermal and UV photo-induced decomposition of azomethane on Rh(111) Kis, Attila; Barthos, Robert; Kiss, Janos Physical Chemistry Chemical Physics, Vol. 2, Issue 18 https://doi.org/10.1039/b003846f	journal	January 2000
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
Comparison of experimental and calculated infrared spectra of aminocarbynes on the Pt(111) surface Chatterjee, Bappaditya; Kang, Dae-Hyuk; Herceg, Eldad The Journal of Chemical Physics, Vol. 119, Issue 20 https://doi.org/10.1063/1.1621624	journal	November 2003
Internal vibrational modes and hydrogen bonding in mixed crystals of HCN and DCN Friedrich, H. B.; Krause, P. F. The Journal of Chemical Physics, Vol. 59, Issue 9 https://doi.org/10.1063/1.1680710	journal	November 1973
The Measurement of Bond Moments and Derivatives in HCN and DCN from Infrared Intensities Hyde, G. E.; Hornig, D. F. The Journal of Chemical Physics, Vol. 20, Issue 4 https://doi.org/10.1063/1.1700508	journal	April 1952
The Infra‐Red Spectrum of Solid Hydrogen Cyanide Hoffman, Robert E.; Hornig, D. F. The Journal of Chemical Physics, Vol. 17, Issue 11 https://doi.org/10.1063/1.1747132	journal	November 1949
Formation of hydrogen bonded aggregates of aminomethylidyne on Pt(111) Jentz, D.; Mills, P.; Celio, H. The Journal of Chemical Physics, Vol. 105, Issue 8 https://doi.org/10.1063/1.471840	journal	August 1996
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 111, Issue 15 https://doi.org/10.1063/1.480097	journal	October 1999
Modeling proton mobility in acidic zeolite clusters: II. Room temperature tunneling effects from semiclassical rate theory Fermann, Justin T.; Auerbach, Scott The Journal of Chemical Physics, Vol. 112, Issue 15 https://doi.org/10.1063/1.481318	journal	April 2000
Infrared Absorption Spectrum of Hydrogen Cyanide Choi, Kyu Nam; Barker, E. F. Physical Review, Vol. 42, Issue 6 https://doi.org/10.1103/PhysRev.42.777	journal	December 1932
High-precision sampling for Brillouin-zone integration in metals Methfessel, M.; Paxton, A. T. Physical Review B, Vol. 40, Issue 6 https://doi.org/10.1103/PhysRevB.40.3616	journal	August 1989
Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111) Neugebauer, Jörg; Scheffler, Matthias Physical Review B, Vol. 46, Issue 24 https://doi.org/10.1103/PhysRevB.46.16067	journal	December 1992
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
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
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals Hammer, B.; Hansen, L. B.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/PhysRevB.59.7413	journal	March 1999
Van der Waals density functionals applied to solids Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos Physical Review B, Vol. 83, Issue 19 https://doi.org/10.1103/PhysRevB.83.195131	journal	May 2011
VESTA : a three-dimensional visualization system for electronic and structural analysis Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 41, Issue 3 https://doi.org/10.1107/S0021889808012016	journal	May 2008
An object-oriented scripting interface to a legacy electronic structure code Bahn, S. R.; Jacobsen, K. W. Computing in Science & Engineering, Vol. 4, Issue 3 https://doi.org/10.1109/5992.998641	journal	January 2002
Anharmonic Potential Constants and Vibrational and Rotational Parameters for Hydrogen Cyanide Nakagawa, Toru; Morino, Yonezo Bulletin of the Chemical Society of Japan, Vol. 42, Issue 8 https://doi.org/10.1246/bcsj.42.2212	journal	August 1969
UV–Vis Light-induced Aging of Titan’s Haze and Ice Couturier-Tamburelli, Isabelle; Piétri, Nathalie; Letty, Vincent Le The Astrophysical Journal, Vol. 852, Issue 2 https://doi.org/10.3847/1538-4357/aa9e8d	journal	January 2018
Van der Waals density functionals applied to solids Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos arXiv https://doi.org/10.48550/arxiv.1102.1358	text	January 2011

Similar Records

Adsorption of sulfur on bimetallic surfaces: Formation of copper sulfides on Pt(111) and Ru(001)

Journal Article · Mon May 01 00:00:00 EDT 1995 · Journal of Vacuum Science and Technology, A · OSTI ID:57126

Adsorption of sulfur on bimetallic surfaces: Formation of copper sulfides on Pt(111) and Ru(001)

Technical Report · Mon Oct 31 23:00:00 EST 1994 · OSTI ID:10191271

Vibrational and electronic spectra of the H + HCN reaction products trapped in solid argon

Journal Article · Wed Dec 30 23:00:00 EST 1987 · J. Phys. Chem.; (United States) · OSTI ID:5249550

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Reaction pathways for HCN on transition metal surfaces

Citation Formats

References (54)

Similar Records

Related Subjects