NITRIC-OXIDE ADSORPTION AND OXIDATION ON Pt (111) IN ELECTROLYTE SOLUTION UNDER POTENTIAL CONTROL A Term Paper Submitted in Partial Fulfilment

for the Requirement of M.Sc. 1 st Part Examination in Chemistry

Submitted by: S.P. Adhikari Roll No. 32/067

Submitted to Central Department of Chemistry Institute of Science and Technology Tribhuwan University Kirtipur, Kathmandu Nepal

Contents Page

List Of Abbreviations Abstract 1. Introduction 2. Literature Survey 3. Experimental section 4. Results and Discussion 5. Conclusion 6. Suggestion for further work 7. References 8. Acknowledgement 1 3 5 7 11 12 13 14

LIST OF ABBREVIATIONS: -

NO NEXAFS XPS LEED STM UHV RT SXRD

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Nitric oxide Near Edge X-ray Absorption fine Structure Spectroscopy X-ray Photoelectron Spectroscopy Low Energy Diffraction Scanning Tunneling Microscopy Ultra High Vacuum Room Temperature Synchrotron X-ray Diffraction

ABSTRACT: NO molecules adsorbed on a Pt(111) surface from dipping in an acidic nitrite solution are studied by near edge X-ray absorption fine structure spectroscopy (NEXAFS),infrared reflection X-ray photoelectron spectroscopy (XPS),low energy electron diffraction (LEED), scanning tunneling microscopy (STM) techniques. LEED patterns and STM images show that no long range ordered structures are formed after NO adsorption on a Pt(111) surface. Although the total NO coverage is very low, spectroscopic features in N K-edge and OK-edge absorption spectra have been singled out and related to the different species induced by this preparation method. From these measurements it is concluded that the NO molecule is adsorbed trough the N atom in an upright conformation. When NO molecules adsorb on a surface at a low temperature (11 K), each molecule transiently migrates on the surface from the first impact point to a possible adsorption site. The maximum saturation coverage is about 0.3 monolayer, and although nitric oxide is the major component, nitrite and nitrogen species are slightly co-adsorbed on the surface. The results obtained from this study are compared with those previously reported in the literature for NO adsorbed on Pt(111) under UHV conditions.

1. INTRODUCTION : Nitrogen Oxides (NO, NO2.. NOX ) have been studied extensively because they are nowadays among the most common pollutants, being harmful to the human respiratory organ and nervous system as well as the major component of Photochemical smog [1, 2].In particular, nitric oxide has received considerable attention in the last years because of its important role in human body. Besides, NO adsorption on metal surface is of relevance for many catalytic and electro-catalytic processes. Nitric oxide is a strong pollutant and one of the major components of automotive exhaust gases. It is necessary to develop the techniques which will allow us to capture NO. The removal of this harmful component is commonly achieved by the use of catalytic materials, such as platinum, which allows the catalytic conversion of the hazardous NOx species to innoxious reaction products. The studies of NO adsorption on well-defined platinum surfaces are usually carried out either from the gas phase in Ultra High Vacuum (UHV) environments or from a solution in an electrochemical cell. In the latter case, the adsorption is performed from a solution saturated with NO gas (or from acid solution of nitrite ions)[3]. In the last few years a great interest has been paid to the use of surface science characterization techniques such as Near Edge x-ray Adsorption Fine Structure Spectroscopy (NEXAFS) to gather insights into non-perfect systems. This is particularly true for structures prepared in aqueous conditions. Due to its extremely low cost, layers prepared in this environment are more suitable for technological applications than those prepared in ultra high vacuum (UHV) conditions. All recent works concerning NO adlayers formed in UHV conditions conclude that NO adsorbs molecularly between 100 and 375 K, with the N atom bound to the Pt surface, and with a small tilt of the molecular axis with respect to the surface normal. Over this range of temperatures, many different phases and adsorption sites have been reported. However, it seems clear that the saturation coverage at RT is about 0.5 ML. On the other hand, studies concerning adsorption of NO on Pt(111) from solution using NEXAFS conclude that NO can adsorb molecularly either from a solution saturated with NO gas or from an acid solution of nitrite ions, leading to saturation coverage smaller than 0.5 ML.

2.LITERATURE SURVEY First studied in 1772 by Joseph Priestly, who called it "nitrous air," nitric oxide was first discovered as a colorless, toxic gas. It was observed as a substance produced during the lightening of the thunderstorm which is the cause of acid rain. Later it was observed to be one of the pollutant and by-product of the combustion of substance in air, as in automobile engines, fossil fuel power plants [3]. It was also found as a important cellular signaling molecule involved in many physiological and pathological processes. It is a powerful vasodilator with a short halflife of a few seconds in the blood. Long-known pharmaceuticals like nitroglycerine and amyl nitrite were discovered, more than century after their first use in medicine, to be active through the mechanism of being precursors to nitric oxide. Low levels of nitric oxide production are important in protecting organs such as the liver from ischemic damage [4].However environmental concern, such as global climate changes, depletion of ozone layer and challenging environmental issue facing the world community have motivated intensive research on NO capture and sequestration, increases. Mainly researches were focused on capture of NO from automobile exhaust. In past adsorption of nitric oxide was firstly achieved by Ultra High Vacuum (UHV) method. But its only possible for large stationary source of NO and highly expensive. Furthermore the adsorption can be achieved in fewer amounts by UHV. So that, many researches are followed to achieve inexpensive and low energy penalties with greater adsorption on the surface of the metal. Structural investigation of NO on pt(111) surface conclude that the best result can be achieved with electrolyte solution under potential control, than all the other methods available. In this research the adsorption of NO on Pt(111) surface with different chemical compositions were done.

3. EXPERIMENTAL SECTION: 3.1. Cyclic voltammetry The working electrode was a 10 mm diameter Pt(111) single-crystal disk (oriented to 0.5) and as supporting electrolyte we used 0.5 M H2SO4.The electrode pretreatment consisted of heating the crystal to 1000 C in a gas/oxygen flame for 3min and then allowing it to cool for 60 s in the vapor of de-aerated supporting electrolyte before quenching it in the same solution. Surface cleanliness and ordering was determined by cyclic voltammetry in 0.5 M H2SO4. Voltammograms of the clean Pt(111) show the characteristic butterfly shape first described by Clavilier [5]. Rinsing of the electrode and/or solution exchange was carried out in a flow-through fashion inside the cell without exposing the electrode to the environment. The reference electrode was Hg/Hg2SO4/0.5 MH2SO4. A platinum foil was used as counter electrode.

3.2. X-ray diffraction and X-ray photoemission The SXRD experiments were performed at theID32 beam line at European Synchrotron Radiation Facility in Grenoble. The X-ray energy was chosen at E=19 keV (=0.65060 ).We used an electrochemical cell simultaneously fulfilling the requirements for all electrochemical experiments and for in situ SXRD [6]. After mounting the sample in the cell, a 6-lm-thickmylar window was installed. The cell was filled with de-aerated electrolytes and the mylar window inflated by a slight overpressure yielding a several mm-thick sheet of electrolyte above the sample. The fitting of the CTR has been performed by a least-square approach [7]. The NO Pt(111) interface was simulated starting from a bulk-like surface model. Due to their lower scattering power, the N and O contributions to the simulated CTR turned out to be negligible. The parameters involved in the fitting procedure were related to the scale factor, the surface roughness (b) and the relaxation of the Pt top-most layer. The ex situ photoemission experiments were carried out in an UHV chamber. The chamber is equipped with a double-pass cylinder mirror analyzer. A Mg anode in the X-ray source was used for experiments (1253.6 eV photons). The energy resolution is about 0.9 eV.

3.3. Overlayer preparation and experimental method NO adlayers on Pt(111) have been produced by means of two different pathways. The first method consists of generating the NO over layer on Pt(111) from an acidic solution of nitrite.

The nitrite solutions (110-3 M) were prepared from supra pure KNO2 and sulfuric acid H2SO4. Alternatively, the NO adlayers were performed by adsorption from a standard saturated NO solution prepared by bubbling NO gas through oxygen-free H2SO4 solutions for 30 min. The surface preparation of the Pt(111) immediately prior to the diffraction or XPS measurements consisted of several steps. After recording the characteristic voltammogram of the Pt(111) electrode in 0.5 M H2SO4, this solution was replaced by either a 1 mm KNO2+0.5 M H2SO4 solution or a saturated NO gas solution (depending on the way choose to generate the adlayer) in a flow-through fashion inside the cell. The electrode was held at open circuit potential for 30 min in contact with the solution. The pretreated Pt(111) surface was removed and mounted in the SXRD cell or introduced in the XPS system. During the transport from the electrochemical preparation cell, the samples were protected against air by allowing a small drop of solution to remain on the sample surface. The X-ray diffraction cell was filled with a 1 mm KNO2+ 0.5 M H2SO4 solution or a saturated NO gas solution and the electrode were held in contact with the solution during the measurements.

4. EXPERIMENTAL RESULTS AND DISCUSSION 4.1. Electrochemical characterization

Fig. 1 shows a voltammogram with two consecutive scans obtained in 0.5 M H2SO4. Previously, the NO adlayer on Pt(111) was generated by dipping the electrode at open circuit in a saturated nitric oxide solution in the way described above. This curve shows in the scan toward anodic potential two oxidation peaks at +0.95 and +1.01V. In the cathodic direction, two reduction peak scan be distinguished at +0.95 and +0.65 V as well as a shoulder at approximately +0.77 V. The oxidation peaks are associated with the following process: NOads+H2O NO2Hads+H++1e-

NO2HadsNO2ads+H++1eThe oxidation charge has been estimated for different scan rates, and it has been found that its value diminishes when the scan rate () increases, indicating that the oxidation process of adsorbed species is very low. At <50 mVs-1 a 128 cm-2 charge value is obtained, being equivalent to about 0.25 ML for the two-electron transfer process described above.

4.2. Nature of the deposited species Fig. 3 shows the XPS photoemission peaks of the N1s core level recorded for the two different adsorption procedures described in the experimental details section. The upper peak has been obtained from a KNO2solution whereas the lower by bubbling NO gas in the electrolyte. The vertical dashed lines on the figure represent the reported binding energies for adsorbed N2 (~398 eV), NO (~401 eV) and NO2. The binding energies of the first two species were taken from a study on Pt-(111) in UHV (see Ref. [8], and references therein).Although we have not found any published reference for NO2 on Pt(111), by charge and thermodynamic arguments one could expect it at least 1 eV shifted towards higher binding energies, that is, around 402.5 eV [11]. The energy difference between these two species is more than the experimental resolution and therefore they can be resolved from the spectra. The maxima of the XPS peaks in Fig. 3 appear at the same binding energy for both deposition procedures, indicating that the adsorbed species are present in the same chemical state. Furthermore, the binding energy of the peak maxima is close to the reported value for NO adsorbed on Pt(111) in UHV. Therefore we can conclude that NO adsorbs molecularly and without dissociation on the Pt(111) surface, as it has been already suggested [12]. Note, however, that a dissociation of the (NO2) has to take place in order to adsorb as NO if the adsorption is performed from the KNO2solution.The peaks in Fig. 3 are broader than the ones reported for UHV preparation suggesting that several species coexist on the surface in the electrochemical preparation. Wider peaks could be related to different atomic adsorption sites and also to some adsorption at step edges or at terrace boundaries. We have quantified the total amount of NO on the surface by XPS using a model to derive concentrations of patched over layer on a semi-infinite substrate. We have found that the total coverage is around 0.2 layers. This small value is at the limit of detection of the technique and agrees with the charge flow estimation from the voltammograms and with previously reported values [13].

Fig. 3. N1s core level photoemission peak of the Pt(111) surface after NO adsorption by different procedures.

5. CONCLUSIONS Flame-annealing and electrochemical preparation of the Pt(111) surface leads to wide terraces where ordered NO adsorption could take place. Analysis of the XPS N1s core level peak reveals that NO adsorbs molecularly on the Pt(111) surface from a solution. However, the large width of the N1s XPS peak and the absence of fractional order X-ray diffracted beams indicate the lack of long-range order for the adsorption process. Furthermore, in situ oxidation of the NO leads to an increase of the surface roughness, this is likely occurring because some Pt atoms are squeezed out of the surface plane.

6. SUGGESTION FOR FURTHER WORK : The Global climate change is one of the hot topics of our concern. To get our earth alive, we should control in the emission of Green House Gases, which will be the milestone in the field of climate change. As we know burning of fossil fuel and automobiles are necessary parts of our life. So we cant stop the use of fossil fuels and automobiles but it is necessary to achieve the technologies that capture the NO emission from the sources. Many practices from past decades have been done. It is necessary to achieve the technologies that capture the NO inexpensive and low energy penalties. The use of such electrolytic solutions under some potential control can be a significant method for the capture of NO from automobile exhaust. Consequently reduce NO level in atmosphere. Such type of research using nitrite solution should be done in near future.

7. REFERENCE : 1) R.Blake, Decomposition of Nitric Oxide from Car Exhaust, Research Seminar Massachusetts Academy of Math and Science, 7-10,February 14, 2008. 2) R.D.Madan, Advanced Inorganic Chemistry, Vol-2, 1995. 3) www.wikipedia.org. 4) American Journal of Respiratory and Critical care medicine, vol. 171, 913, 2005. 5) J. Clavilier, J. Electroanal. Chem. 107-211, 1980. 6) J. Ziegler, O. Bunk, G. Scherb, A. Kazimirov, L.X Cao, J. Zegenhagen, Surf. Sci. vol 346, 352-354, 1996. 7) E. Vlieg, J. Appl. Crystallogr. vol. 33, 401-405, 2000. 8) F. Borgatti, R. Felici, submitted for publication. 9) K. Momoi, M.B. Song, M. Ito, J. Electroanal. Chem. vol. 473, 43, 1999. 10) Z-H. Zang, Z.-L. Wu, S.-L. Yau, J. Phys. Chem. B vol. 103, 9624, 1999. 11) S. Hufner, Photoelectron Spectroscopy, Springer Series in Surface Science, 1995. 12) A. Rodes, R. Gomez, J.M. Perez, J.M. Feliu, A. Aldaz, J. Electrochem. vol 41, 729,1996. 13) M. Kiskinova, G. Pirug, H.P. Bonzel, Surf. Sci. 136-285, 1984. 14) N. Matere, A. Barbieri, D. Gardin, U. Starke, J.D. Batteas, M.A. Van Hove, G.A. somorjai, Surf.Sci. vol. 303, 319, 1994. 15) H. You, D.J. Zurawski, Z. Nagy, R.M. Yonco, J. Chem. Phys. vol. 100, 4699, 1994.

8. ACKNOWLEDGEMENT : I am happy to acknowledge the valuable guidance of my respected teacher Associate Prof. Dr. Kedar Nath Ghimire Central Department of Chemistry, T.U., Kirtipur. Finally, I am greatly indebted to by friends Krishna Gnawali and Pradeep Subedi who provided me different materials to make me able to finish this term paper, especially Pradhan-link for providing me free internet facility.