In situ ATR-FTIRS coupled with on-line DEMS under controlled mass transport conditions—A novel tool for electrocatalytic reaction studies

Room Temperature COad Desorption/Exchange Kinetics on Pt Electrodes—A Combined In Situ IR and Mass Spectrometry Study

“…[3] Herein, we investigated the exchange and desorption of CO ad and, in particular, its kinetics in equilibrium with CO containing electrolyte, using isotope labeling techniques ( 13 CO) and an advanced experimental setup, which allows the simultaneous identification and quantitative determination of adsorbed species, volatile reaction products/educts and overall reaction rates under well-defined reaction conditions and under enforce electrolyte transport. [9,10] First we will present time-resolved sequences of IR spectra which clearly show that 13 CO ad is rapidly exchanged by 12 CO ad when gas-phase 12 CO is present in the electrolyte and that the time for complete exchange depends on the concentration of the 12 CO. For a quantitative evaluation of the exchange rate and the resulting 13 CO/ 12 CO fractional coverages we employed online differential electrochemical mass spectrometry (DEMS), following the desorption of 13 CO during exposure of a 13 CO pre-saturated Pt film electrode to 12 CO in a continuous flow of 12 CO containing electrolyte. Changes in the CO adlayer composition were simultaneously followed by in situ IR spectroscopy under identical conditions, which provides additional mechanistic information on the CO ad exchange process.…”

Ethanol oxidation on shape-controlled platinum nanoparticles at different pHs: A combined in situ IR spectroscopy and online mass spectrometry study

“…A more detailed description of this flow-cell configuration was previously given in [31]. In brief, the central cell Au film was prepared by electroless deposition following the procedure reported previously [32][33][34].…”

Numerical Partitioning Model for the Koutecký-Levich Analysis of Electrochemical Flow Cells with a Combined Channel/Wall-Jet Geometry

“…Nevertheless, a linear summation of Eq. 2 and 3, weighted by R A according to Figure 5, leads to the following equation separating kinetic and mass transport determined currents: [10] which, after simplification, yields:…”

“…[1][2][3][4] Also in electrocatalysis, flow cells have been employed offering the possibility to work at elevated temperature and pressure, [5][6][7] further enhanced by the coupling to spectroscopic tools. [8][9][10][11] Other designs emphasize gas dosing by upstream mixing of two electrolytes, 12,13 implementation of quartz crystal microgravimetry 14,15 or the combination with in-situ X-ray absorption spectroscopy [16][17][18][19][20] or scattering techniques. [20][21][22][23] Recently, a new class of electrochemical flow cells emerged from scanning electrochemical microscopes 24,25 and scanning droplet cells, [26][27][28] termed scanning flow cells (SFCs) or scanning droplet cell microscopes (SDCMs).…”