NANOGAP-ENABLED STUDY OF ELECTRODE REACTIONS BY SCANNING ELECTROCHEMICAL MICROSCOPY

NANOGAP-ENABLED STUDY OF ELECTRODE REACTIONS BY SCANNING ELECTROCHEMICAL MICROSCOPY Nikoloz Nioradze, PhD University of Pittsburgh, 2014 The nanogap quasi-steady-state voltammetry, developed in my work, presents the way to monitor and study rapid electron transfer reactions on macroscopic substrates of scanning electrochemical microscopy (SECM). It combines the cyclic voltammetry and SECM and monitors substrate reaction as a tip current. The resulting plot of iT versus ES features the retraceable sigmoidal shape of a quasi-steady state voltammogram although a transient peak-shape voltammogram is obtained simultaneously at the macroscopic substrate. This simplifies measurement and analysis of a quasi-steady-state voltammogram and gives information about thermodynamic as well as kinetic parameters of the reaction taking place at the interface. No charging current at the amperometric tip, high and adjustable mass transport under the tip and high spatial resolution are all advantages of quasi-steady-state voltammetry. I also introduced generalized theory for nanoscale iT-ES voltammetry of substrate reactions with arbitrary reversibility and mechanism under comprehensive experimental conditions including any substrate potential and both SECM modes (feedback and substrate generation tip collection, SG/TC). I nanofabricated submicrometer size highly reliable Pt SECM tips and found the way of protection of these tiny electrodes from the damage caused either by electrostatic discharge or electrochemical etching. Subsequent application of quasi-steady-state voltammetry and reliable nanofabricated SECM probes enabled sensitive detection of adsorption of organic impurities from air and ultrapure water to the HOPG surface as evidenced by redox reaction of ferrocenylmethyl)trimethyl ammonium (FcTMA+). Study revealed that hydrophobic contaminant layer slows down the access of hydrophilic aqueous redox species to the underlying HOPG surface, thereby yielding a lower standard rate constant, k0. Moreover, this barrier effects stronger to a more charged form (FcTMA2+) of a redox couple so that the electron-transfer reaction of the more hydrophilic form is slower to yield a lower k0 value

DEVELOPMENT OF NANOFABRICATED PROBES FOR SCANNING ELECTROCHEMICAL MICROSCOPY

ABSTRACTNikoloz Nioradze, MSUniversity of Pittsburgh 2009The work describes development of novel Pt disk electrodes with nanometer diameters using focused ion beam (FIB) milling. The nanofabricated electrodes are applied as probes of scanning electrochemical microscopy (SECM) for studying of electrochemical processes on redox reactive substrates. Nanotips are fabricated by pulling a platinum wire sealed in a glass capillary using a laser pipette puller. An inlaid platinum disk eventually is exposed by milling the tip of a pulled capillary by FIB. Electrodes are as small as 300-500 nm in diameter with a ratio of insulating glass sheath and Pt wire (RG) as small as 3. Moreover, FIB milling gives a flat tip surface. The small RG and smooth surface are helpful for approaching a probe close to a substrate in SECM feedback experiments. Nanometer-sized electrodes can be readily positioned within 100 nm from a polished platinum surface. After placing the tip close to the Pt disk, a potential of the Pt substrate is swept to drive a redox reaction, which is monitored as a current response at the nanometer-sized electrode. Presented method of combination of SECM and substrate cyclic voltammetry (CV) will allow for accurate extraction of electrochemical kinetic parameters of a redox reaction. Overall, it can be concluded that tips fabricated by presented method can be successfully exploited for SECM experiments. Described SECM-substrate CV approach will be useful for monitoring of electrochemical behavior of different conductive substrates

Resonance-like coherent production of a pion pair in the reaction pd→pdππpd \rightarrow pd\pi\pi in the GeV region

The reaction $p + d \rightarrow p + d + X$ was studied at 0.8-2.0 GeV proton beam energies with the ANKE magnetic spectrometer at the COSY synchrotron storage ring. The proton-deuteron pairs emerging with high momenta, 0.6-1.8 GeV/$c$, were detected at small angles with respect to the proton beam. Distribution over the reaction missing mass $M_x$ reveals a local enhancement near the threshold of the pion pair production specific for the so-called ABC effect. The enhancement has a structure of a narrow bump placed above a smooth continuum. The invariant mass of the $d\pi\pi$ system in this enhancement region exhibits a resonance-like peak at $M_{d\pi\pi} \approx 2.36$ GeV/$c^2$ with the width $\Gamma \approx 0.10$ GeV/$c^2$. A possible interpretation of these features is discussed.Comment: 14 pages, 16 figures, submitted to Eur. Phys. J. A. v2: Added references [42,43] in section IV.A. v3: revised version according to referee remarks v4: revised version according to referee remark

The Near-Threshold Production of Phi Mesons in pp Collisions

The pp->pp phi reaction has been studied at the Cooler Synchrotron COSY-Juelich, using the internal beam and ANKE facility. Total cross sections have been determined at three excess energies epsilon near the production threshold. The differential cross section closest to threshold at epsilon=18.5 MeV exhibits a clear S-wave dominance as well as a noticeable effect due to the proton-proton final state interaction. Taken together with data for pp omega-production, a significant enhancement of the phi/omega ratio of a factor 8 is found compared to predictions based on the Okubo-Zweig-Iizuka rule.Comment: 4 Pages, 3 Figures, 1 Table, submitted to Phys. Rev. Let

Measurement of the analyzing powers in pd elastic and pn quasi-elastic scattering at small angles

The analyzing powers in proton-deuteron elastic and proton-neutron quasi-elastic scattering have been measured at small angles using a polarized proton beam at the COSY storage ring incident on an unpolarized deuterium target. The data were taken at 796MeV and five higher energies from 1600MeV to 2400MeV. The analyzing power in pd elastic scattering was studied by detecting the low energy recoil deuteron in telescopes placed symmetrically in the COSY plane to the left and right of the beam whereas for pn quasi-elastic scattering a low energy proton was registered in one of the telescopes in coincidence with a fast scattered proton measured in the ANKE magnetic spectrometer. Though the experiment explores new domains, the results are consistent with the limited published information.Comment: 10 pages with 8 figure

First measurements of spin correlations in the np -> d pi^0 reaction

The transverse spin correlations Axx and Ayy in the np-> d pi^0 reaction have been measured for the first time in quasi-free kinematics at the COSY-ANKE facility using a polarised deuteron beam incident on a polarised hydrogen cell target. The results obtained for neutron energies close to 353 MeV and 600 MeV are in good agreement with the partial wave analysis of data on the isospin-related pp-> d pi^+ reaction, though the present results cover also the small-angle region, which was largely absent from these data

Near-threshold production of omega mesons in the pn -> d omega reaction

The first measurement of the p n -> d omega total cross section has been achieved at mean excess energies of Q = 28 and 57 MeV by using a deuterium cluster-jet target. The momentum of the fast deuteron was measured in the ANKE spectrometer at COSY-Juelich and that of the slow "spectator" proton p(sp) from the p d -> p(sp) d omega reaction in a silicon telescope placed close to the target. The cross sections lie above those measured for p p -> p p omega but seem to be below theoretical predictions.Comment: 7 pages, 8 figures; second approach to describe the background has been added; results changed insignificantly, EPJ in pres

Coherent pion production in proton-deuteron collisions

Values of the proton analysing power in the $pd\to{}^{3}\textrm{He}\,\pi^0/^{3}\textrm{H}\,\pi^+$ reactions at 350-360~MeV per nucleon were obtained by using a polarised proton beam incident on a deuterium cluster-jet target and with a polarised deuteron beam incident on a target cell filled with polarised hydrogen. These results have a much larger angular coverage than existing data. First measurements are also presented of the deuteron vector analysing power and the deuteron-proton spin correlations. Data were also obtained on the deuteron-proton spin correlation and proton analysing power at small angles at 600~MeV per nucleon, though the angular coverage at this energy was much more restricted even when using a deuteron beam. By combining the extrapolated values of the spin correlations to the forward or backward directions with published measurements of the deuteron tensor analysing powers, the relative phases between the two non-vanishing amplitudes were evaluated.Comment: 5 pages, 5 figure

Measurement of the Analyzing Power in p⃗d→(pp)n\vec{p}d \to (pp)n \\with a Fast Forward 1S0^1S_0--Diproton

A measurement of the analyzing power $A_y$ of the $\vec{p}d \to (pp) + n$ reaction was carried out at beam energies of 0.5 and 0.8 GeV by detection of a fast forward proton pair of small excitation energy $E_{pp} < 3$ MeV. The kinematically complete experiment made use of the ANKE spectrometer at the internal beam of COSY and a deuterium cluster--jet target. For the first time the $S$--wave dominance in the fast diproton is experimentally demonstrated in this reaction. While at $T_p=0.8$ GeV the measured analyzing power $A_y$ vanishes, it reaches almost unity at $T_p=0.5$ GeV for neutrons scattered at $\theta_n^{c.m.}=167^\circ$. The results are compared with a model taking into account one--nucleon exchange, single scattering and $\Delta$ (1232) excitation in the intermediate state. The model describes fairly well the unpolarized cross section obtained earlier by us and the analyzing power at 0.8 GeV, it fails to reproduce the angular dependence of $A_y$ at 0.5 GeV.Comment: 4 pages, 4 figures, 1 tabl

Measurement of the analysing power in proton-proton elastic scattering at small angles

The proton analysing power in $\vec{p}p$ elastic scattering has been measured at small angles at COSY-ANKE at 796 MeV and five other beam energies between 1.6 and 2.4 GeV using a polarised proton beam. The asymmetries obtained by detecting the fast proton in the ANKE forward detector or the slow recoil proton in a silicon tracking telescope are completely consistent. Although the analysing power results agree well with the many published data at 796 MeV, and also with the most recent partial wave solution at this energy, the ANKE data at the higher energies lie well above the predictions of this solution at small angles. An updated phase shift analysis that uses the ANKE results together with the World data leads to a much better description of these new measurements.Comment: 5 pages, 3 figure