caa a22 4500 475844505 CHVBK 20180406123910.0 cr unu---uuuuu 170329e20000701xx s 000 0 eng 10.1023/A:1009076720641 doi (NATIONALLICENCE)springer-10.1023/A:1009076720641 Modelling alkali promotion in heterogeneous catalysis: in situ electrochemical control of catalytic reactions [Elektronische Daten] [Richard Lambert, Federico Williams, Alejandra Palermo, Mintcho Tikhov] Electron spectroscopic data and reactor measurements show that electrochemical promotion (EP) of thin film catalysts deposited on solid electrolyte supports is the result of spillover phenomena at the three‐phase boundary between the electrolyte, the catalyst and the gas phase. Ions from the electrolyte are discharged at the electrode/electrolyte interface and migrate to cover the catalyst surface whose properties are thereby strongly altered. The EP effect and the phenomena that underlie it are illustrated here by reference to the Na‐promoted catalytic reduction of NO by CO over copper. Electro‐pumping of Na from a β″‐alumina solid electrolyte to the catalyst surface results in large improvements in both activity and selectivity of the latter. Under reaction conditions, the alkali promoter is present as submonolayer amounts of NaNO3 on an oxidised Cu surface. The results indicate that Cu0 sites are not of significance and that the catalytically active surface is dominated by Cu+ and Cu2+ sites. They also show that Cu+ is the critically important site for NO adsorption and that EP is due to Na‐induced enhancement of the adsorption and dissociation of NO at Cu+ sites. Kluwer Academic Publishers, 2000 promotion nationallicence sodium nationallicence electrochemical nationallicence NO reduction nationallicence catalytic nationallicence CO nationallicence copper nationallicence β″‐alumina nationallicence XPS nationallicence Lambert Richard Department of Chemistry, University of Cambridge, CB2 1EW, Cambridge, UK aut Williams Federico Department of Chemistry, University of Cambridge, CB2 1EW, Cambridge, UK aut Palermo Alejandra Department of Chemistry, University of Cambridge, CB2 1EW, Cambridge, UK aut Tikhov Mintcho Department of Chemistry, University of Cambridge, CB2 1EW, Cambridge, UK aut Topics in Catalysis Kluwer Academic Publishers-Plenum Publishers 13/1-2(2000-07-01), 91-98 1022-5528 13:1-2<91 2000 13 11244 https://doi.org/10.1023/A:1009076720641 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1023/A:1009076720641 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Lambert Richard Department of Chemistry, University of Cambridge, CB2 1EW, Cambridge, UK aut NATIONALLICENCE 700 1- Williams Federico Department of Chemistry, University of Cambridge, CB2 1EW, Cambridge, UK aut NATIONALLICENCE 700 1- Palermo Alejandra Department of Chemistry, University of Cambridge, CB2 1EW, Cambridge, UK aut NATIONALLICENCE 700 1- Tikhov Mintcho Department of Chemistry, University of Cambridge, CB2 1EW, Cambridge, UK aut NATIONALLICENCE 773 0- Topics in Catalysis Kluwer Academic Publishers-Plenum Publishers 13/1-2(2000-07-01), 91-98 1022-5528 13:1-2<91 2000 13 11244 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer