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Nitrate adsorption and reduction on Cu(100) in acidic solution is studied by electrochemical methods, in situ electrochemical scanning tunneling microscopy (EC-STM), surface enhanced Raman spectroscopy (SERS), and density functional theory (DFT) calculations. Electrochemical results show that reduction of nitrate starts at -0.3 V vs Ag/AgCl and reaches maximum value at -0.58 V. Over the entire potential region interrogated adlayers composed of nitrate, nitrite, or other intermediates are observed by using in situ STM. From the open-circuit potential (OCP) to -0.22 V vs Ag|AgCl, the nitrate ion is dominant and forms a (2 x 2) adlattice on the Cu(100) surface while nitrate forms a dominantly c(2 x 2) structure from -0.25 to -0.36 V. The interconversion between the nitrate and nitrite adlattices is observed. DFT calculations indicate that both nitrate and nitrite are twofold coordinated to the Cu(100) surface.

The work exploring the stoichiometry of Pt deposition via surface-limited redox replacement of the underpotentially deposited ͑UPD͒ Cu monolayer on Au͑111͒ is presented. The Cu UPD monolayer is formed from 10 −3 M Cu 2+ + 0.1 M HClO 4 solution, whereas the Pt deposition via surface-limited redox replacement reaction is carried out in 10 −3 M ͕PtCl 6 ͖ 2− + 0.1 M HClO 4 solution at open-circuit potential. Our results indicate that the Pt submonolayers have two-dimensional morphology and linear dependence of their coverage on the amount ͑coverage͒ of the replaced Cu UPD monolayers. Our analysis shows that the oxidation state of Cu during redox replacement reaction is 1+, suggesting that four Cu UPD adatoms are replaced by each deposited Pt adatom. This work stresses the general importance of the anions, determining the stoichiometry of metal deposition reaction via surface-limited redox replacement of the UPD monolayers.

Using the binding energy of OH* and CO* on close-packed surfaces as reactivity descriptors, we screen bulk and surface alloy catalysts for methanol electro-oxidation activity. Using these two descriptors, we illustrate that a good methanol electro-oxidation catalyst must have three key properties: (1) the ability to activate methanol, (2) the ability to activate water, and (3) the ability to react off surface intermediates (such as CO* and OH*). Based on this analysis, an alloy catalyst made up of Cu and Pt should have a synergistic effect facilitating the activity towards methanol electro-oxidation. Using these two reactivity descriptors, a surface PtCu 3 alloy is proposed to have the best catalytic properties of the Pt-Cu model catalysts tested, similar to those of a Pt-Ru bulk alloy. To validate the model, experiments on a Pt(111) surface modified with different amounts of Cu adatoms are performed. Adding Cu to a Pt(111) surface increases the methanol oxidation current by more than a factor of three, supporting our theoretical predictions for improved electrocatalysts.

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