Calorimetric studies of NO on Ni{2 1 1}: criteria for switching from dissociative to molecular adsorption |
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| Institution: | 1. School of Life Science, Changchun Normal University, Changchun 130032, China;2. College of Chemistry and Chemical Engineering, Zhoukou Normal University, Zhoukou 466000, China;3. Key Laboratory of Grain and Oil Processing of Jilin Province, Jilin Business and Technology College, Changchun 130507, China;1. Chair of Nanoelectronics, Technical University of Munich, Theresienstr. 90/I, 80333 Munich, Germany;2. Catalysis Research Center/Wacker-Lehrstuhl für Makromolekulare Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching bei München, Germany;3. Free University of Bozen – Bolzano, Faculty of Science and Technology, Bozen-Bolzano, Italy;1. CESAM & Department of Chemistry, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal;2. Department of Complementary Sciences, College of Health Technology of Coimbra, Rua 5 de Outubro S. Martinho do Bispo Apartado 7006, 3040-854 Coimbra, Portugal;3. BAM Federal Institute for Materials Research and Testing, Department of Analytical Chemistry, Reference Materials, Richard-Willstaetter-Str. 11, D-12489 Berlin, Germany;4. Department of Applied Chemistry and Physics, University of León, Campus de Vegazana, 24071 León, Spain;1. Institute of Functional Biomolecules, State Key Laboratory of Pharmaceutical Biotechnology, Nanjing University, Nanjing 210093, People’s Republic of China;2. Jiangsu Collaborative Innovation Center For Cardiovascular Disease Translational Medicine, School of Pharmacy, Nanjing Medical University, Nanjing, Jiangsu 210029, People’s Republic of China;3. Department of Science, Hetao College, Bayannur 015000, People’s Republic of China |
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| Abstract: | The coverage-dependent heats of adsorption and sticking probabilities in the interaction of nitric oxide with clean and oxygen pre-covered Ni{2 1 1} surfaces have been measured at 300 K using single crystal adsorption calorimetry. The results are consistent with a switch from dissociative to molecular chemisorption at 1 ML of O plus N adatoms. Initial dissociative adsorption is attributed to step sites with a heat of 400 kJ mol−1. When steps are saturated with adatoms, adsorption proceeds molecularly with a heat of 160 kJ mol−1. With 0.24 ML oxygen adatom pre-coverage, the initial heat is only 250 kJ mol−1 and with 0.6 ML oxygen adatom, NO adsorption is only molecular with an initial heat of 160 kJ mol−1. The NO sticking probability behaviour is consistent with this picture, with successive precursor mediated adsorption at step and terrace sites. The inhibition of dissociation above O, or O plus N, adatom coverages of 1 ML is attributed to the strong lateral repulsive interactions between adatoms, which would drive the dissociative heat of adsorption below that of molecular adsorption at higher coverages. |
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