Competing pathways for isocyanate loss from Cu(0 0 1) with co-adsorbed oxygen

E. Z. Ciftlikli; J. Lallo; E. Y.M. Lee; S. Rangan; S. D. Senanayake; B. J. Hinch

doi:10.1016/j.jcat.2012.08.009

Competing pathways for isocyanate loss from Cu(0 0 1) with co-adsorbed oxygen

E. Z. Ciftlikli, J. Lallo, E. Y.M. Lee, S. Rangan, S. D. Senanayake, B. J. Hinch

School of Arts and Sciences, Chemistry & Chemical Biology

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Cu(0 0 1)-bound isocyanate species (NCO _(a ₎) have been prepared with two distinct methods. Isocyanic acid (HNCO) exposures at room temperature resulted in adsorbed NCO ₍ _a) alone. The exposure of Cu(0 0 1) to cyanogen (C ₂N ₂) and O ₂ leads to surfaces displaying co-adsorbed oxygen (O _(a)), cyanide (CN _(a)), and NCO _(a ₎ species. O ₂ exposure of submonolayer NCO/Cu(0 0 1), followed by brief annealing at 473 K, initiated NCO _(a ₎ oxidation, giving rise to CO _2(g) desorption and a surface-bound atomic N _(a) species. CO _2(g) evolution was observed over a wide range of initial O _(a) coverages. In contrast, comparable thermal treatments of CN + O + NCO/Cu(0 0 1) samples, at 473 K, yield both CO _(g) and CO _2(g). Both TPRD and XPS studies of pre- and post-annealed surfaces indicated the two gaseous products. The co-adsorption of CN _(a) promotes the dissociation of NCO _(a) into CO _(g) and N _(a), and dissociation can become the dominant means for NCO _(a) removal.

Original language	English (US)
Pages (from-to)	269-273
Number of pages	5
Journal	Journal of Catalysis
Volume	295
DOIs	https://doi.org/10.1016/j.jcat.2012.08.009
State	Published - Nov 2012

All Science Journal Classification (ASJC) codes

Catalysis
Physical and Theoretical Chemistry

Keywords

Copper
Cyanide
Dissociation
Isocyanate
Oxidation
Surfaces

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10.1016/j.jcat.2012.08.009

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@article{7d13f0b62df64c618b1cae426015f0e8,

title = "Competing pathways for isocyanate loss from Cu(0 0 1) with co-adsorbed oxygen",

abstract = "Cu(0 0 1)-bound isocyanate species (NCO (a )) have been prepared with two distinct methods. Isocyanic acid (HNCO) exposures at room temperature resulted in adsorbed NCO ( a) alone. The exposure of Cu(0 0 1) to cyanogen (C 2N 2) and O 2 leads to surfaces displaying co-adsorbed oxygen (O (a)), cyanide (CN (a)), and NCO (a ) species. O 2 exposure of submonolayer NCO/Cu(0 0 1), followed by brief annealing at 473 K, initiated NCO (a ) oxidation, giving rise to CO 2(g) desorption and a surface-bound atomic N (a) species. CO 2(g) evolution was observed over a wide range of initial O (a) coverages. In contrast, comparable thermal treatments of CN + O + NCO/Cu(0 0 1) samples, at 473 K, yield both CO (g) and CO 2(g). Both TPRD and XPS studies of pre- and post-annealed surfaces indicated the two gaseous products. The co-adsorption of CN (a) promotes the dissociation of NCO (a) into CO (g) and N (a), and dissociation can become the dominant means for NCO (a) removal.",

keywords = "Copper, Cyanide, Dissociation, Isocyanate, Oxidation, Surfaces",

author = "Ciftlikli, {E. Z.} and J. Lallo and Lee, {E. Y.M.} and S. Rangan and Senanayake, {S. D.} and Hinch, {B. J.}",

note = "Funding Information: The work was funded by the NSF award CHE-0718055 and in part by CHE-1124879. The U12a beamline was supported by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy, under contract DE-AC05-00OR22725 with Oak Ridge National Laboratory. SDS was funded through the ORNL directly. The National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. ",

year = "2012",

month = nov,

doi = "10.1016/j.jcat.2012.08.009",

language = "English (US)",

volume = "295",

pages = "269--273",

journal = "Journal of Catalysis",

issn = "0021-9517",

publisher = "Academic Press Inc.",

}

TY - JOUR

T1 - Competing pathways for isocyanate loss from Cu(0 0 1) with co-adsorbed oxygen

AU - Ciftlikli, E. Z.

AU - Lallo, J.

AU - Lee, E. Y.M.

AU - Rangan, S.

AU - Senanayake, S. D.

AU - Hinch, B. J.

N1 - Funding Information: The work was funded by the NSF award CHE-0718055 and in part by CHE-1124879. The U12a beamline was supported by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy, under contract DE-AC05-00OR22725 with Oak Ridge National Laboratory. SDS was funded through the ORNL directly. The National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

PY - 2012/11

Y1 - 2012/11

N2 - Cu(0 0 1)-bound isocyanate species (NCO (a )) have been prepared with two distinct methods. Isocyanic acid (HNCO) exposures at room temperature resulted in adsorbed NCO ( a) alone. The exposure of Cu(0 0 1) to cyanogen (C 2N 2) and O 2 leads to surfaces displaying co-adsorbed oxygen (O (a)), cyanide (CN (a)), and NCO (a ) species. O 2 exposure of submonolayer NCO/Cu(0 0 1), followed by brief annealing at 473 K, initiated NCO (a ) oxidation, giving rise to CO 2(g) desorption and a surface-bound atomic N (a) species. CO 2(g) evolution was observed over a wide range of initial O (a) coverages. In contrast, comparable thermal treatments of CN + O + NCO/Cu(0 0 1) samples, at 473 K, yield both CO (g) and CO 2(g). Both TPRD and XPS studies of pre- and post-annealed surfaces indicated the two gaseous products. The co-adsorption of CN (a) promotes the dissociation of NCO (a) into CO (g) and N (a), and dissociation can become the dominant means for NCO (a) removal.

AB - Cu(0 0 1)-bound isocyanate species (NCO (a )) have been prepared with two distinct methods. Isocyanic acid (HNCO) exposures at room temperature resulted in adsorbed NCO ( a) alone. The exposure of Cu(0 0 1) to cyanogen (C 2N 2) and O 2 leads to surfaces displaying co-adsorbed oxygen (O (a)), cyanide (CN (a)), and NCO (a ) species. O 2 exposure of submonolayer NCO/Cu(0 0 1), followed by brief annealing at 473 K, initiated NCO (a ) oxidation, giving rise to CO 2(g) desorption and a surface-bound atomic N (a) species. CO 2(g) evolution was observed over a wide range of initial O (a) coverages. In contrast, comparable thermal treatments of CN + O + NCO/Cu(0 0 1) samples, at 473 K, yield both CO (g) and CO 2(g). Both TPRD and XPS studies of pre- and post-annealed surfaces indicated the two gaseous products. The co-adsorption of CN (a) promotes the dissociation of NCO (a) into CO (g) and N (a), and dissociation can become the dominant means for NCO (a) removal.

KW - Copper

KW - Cyanide

KW - Dissociation

KW - Isocyanate

KW - Oxidation

KW - Surfaces

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UR - http://www.scopus.com/inward/citedby.url?scp=84867577794&partnerID=8YFLogxK

U2 - 10.1016/j.jcat.2012.08.009

DO - 10.1016/j.jcat.2012.08.009

M3 - Article

AN - SCOPUS:84867577794

SN - 0021-9517

VL - 295

SP - 269

EP - 273

JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Competing pathways for isocyanate loss from Cu(0 0 1) with co-adsorbed oxygen

Abstract

All Science Journal Classification (ASJC) codes

Keywords

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