Carbon-oxygen bond strength as a control of reaction kinetics: Phenol on Mo(110) |
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| Institution: | 1. Department of Optics and Quantum Electronics, University of Szeged, Szeged, H-6720, Hungary;2. MTA-SZTE Research Group on Photoacoustic Spectroscopy, University of Szeged, Szeged, H-6720, Hungary;3. Department of Oral Biology and Experimental Dental Research, University of Szeged, Szeged, H-6720, Hungary;1. Key Laboratory of Advanced Functional Materials of Nanjing, Nanjing Xiaozhuang University, Nanjing 211171, China;2. Key Laboratory for Organic Electronics and Information Displays, Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China;1. Universidade Federal de Minas Gerais, Departamento de Química, ICEx, Av. Antônio Carlos, 6627, 31270901 Belo Horizonte, MG, Brazil;2. University Toulouse, ENSIACET, UPS INP LCC, Lab Chim Coordinat, UPR 8241, CNRS, 4 Allee Emile Monso, BP 44362, F-31030 Toulouse, France;1. State Key Laboratory of Chemical Engineering (Tianjin University), Tianjin Key Laboratory of Applied Catalysis Science and Technology, School of Chemical Engineering, Tianjin University, Tianjin 300072, China;2. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, China;1. Department of Nano- and Biomedical Technologies, Saratov State University, 83 Astrakhanskaya Str., Saratov 410012, Russia;2. Education and Research Institute of Nanostructures and Biosystems, Saratov State University, Astrakhanskaya, 83, Saratov 410012, Russia;3. Babylon University, Babylon, Iraq;4. Institute of Chemistry, Saratov State University, 83 Astrakhanskaya Str., Saratov 410012, Russia;1. Universidad San Francisco de Quito (USFQ), Grupo de Química Computacional y Teórica (QCT-USFQ), Dpto. de Ingeniería Química, Quito 17-1200-841, Ecuador;2. Universidad San Francisco de Quito (USFQ), Instituto de Simulación Computacional (ISC-USFQ), Diego de Robles y Via Interoceanica, Quito 17-1200-841, Ecuador;3. Universidad de Los Andes (ULA), Departamento de Química, Facultad de Ciencias, La Hechicera, Mérida 5101, Venezuela |
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| Abstract: | The reaction of phenol on Mo(110) has been studied using temperature programmed reaction and X-ray photoelectron spectroscopies. After desorption of multilayers and a weakly bound molecular species, decomposition produces the only reaction products observed: gaseous dihydrogen, surface carbon and surface oxygen. The O-H bond cleaves first at temperatures below 360 K to form surface phenoxide (C6H5O-), followed by C-H bond activation commencing at 370 K. C-O bonds are cleaved in the temperature range of 370 to 450 K. After annealing to 300 K, multiple species are detected on the surface by X-ray photoelectron spectroscopy. The cleavage of C-H bonds in the same temperature regime as C-O bonds is thought to lead to selective decomposition of phenol on Mo(110). The reaction of phenol is contrasted to that of a sulfur-containing analogue, benzenethiol, on the Mo(110) surface. The stability of the phenoxide intermediate with respect to carbon-heteroatom bond cleavage is greater than that of the corresponding phenyl thiolate formed from benzenethiol. Comparison of the reaction of phenol and benzenethiol demonstrates the importance of C-X (X = O,S) bond strength in determining the reactivity and selectivity of these molecules. |
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