Replication Data for: Mapping Proton and Carbon Dioxide Electrocatalytic Reductions at a Rh Complex by In Situ Spectroelectrochemical NMR (ICPSR doi:10.26165/JUELICH-DATA/KJN10U)

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Document Description

Citation

Title:

Replication Data for: Mapping Proton and Carbon Dioxide Electrocatalytic Reductions at a Rh Complex by In Situ Spectroelectrochemical NMR

Identification Number:

doi:10.26165/JUELICH-DATA/KJN10U

Distributor:

Jülich DATA

Date of Distribution:

2025-12-03

Version:

1

Bibliographic Citation:

Kick, Anne-Christine; Schatz, Michael; Kahl, Christian; Hölscher, Markus; Eichel, Rüdiger-A.; Granwehr, Josef; Kaeffer, Nicolas; Leitner, Walter, 2025, "Replication Data for: Mapping Proton and Carbon Dioxide Electrocatalytic Reductions at a Rh Complex by In Situ Spectroelectrochemical NMR", https://doi.org/10.26165/JUELICH-DATA/KJN10U, Jülich DATA, V1

Study Description

Citation

Title:

Replication Data for: Mapping Proton and Carbon Dioxide Electrocatalytic Reductions at a Rh Complex by In Situ Spectroelectrochemical NMR

Identification Number:

doi:10.26165/JUELICH-DATA/KJN10U

Authoring Entity:

Kick, Anne-Christine (ITMC RWTH Aachen University, MPI CEC)

Schatz, Michael (IET-1 Forschungszentrum Jülich GmbH, ITMC RWTH Aachen University)

Kahl, Christian (MPI CEC)

Hölscher, Markus (ITMC RWTH Aachen University)

Eichel, Rüdiger-A. (IET-1 Forschungszentrum Jülich GmbH, IPC RWTH Aachen University, Faculty of Mechanical Engineering RWTH Aachen University)

Granwehr, Josef (IET-1 Forschungszentrum Jülich GmbH, ITMC RWTH Aachen University)

Kaeffer, Nicolas (MPI CEC, LIMA CNRS Université de Strasbourg)

Leitner, Walter (ITMC RWTH Aachen University, MPI CEC)

Other identifications and acknowledgements:

Kick, Anne-Christine

Other identifications and acknowledgements:

Schatz, Michael

Other identifications and acknowledgements:

Hölscher, Markus

Other identifications and acknowledgements:

Eichel, Rüdiger-A.

Other identifications and acknowledgements:

Granwehr, Josef

Other identifications and acknowledgements:

Kaeffer, Nicolas

Other identifications and acknowledgements:

Leitner, Walter

Software used in Production:

TopSpin

Software used in Production:

Python

Software used in Production:

NMRglue

Software used in Production:

EC-Lab

Grant Number:

390919832

Distributor:

Jülich DATA

Access Authority:

Kick, Anne-Christine

Access Authority:

Schatz, Michael

Access Authority:

Granwehr, Josef

Depositor:

Schatz, Michael

Date of Deposit:

2025-01-13

Study Scope

Keywords:

Chemistry

Abstract:

Results of spectroelectrochemical NMR and UV-Vis experiments, described in the publication: Kick A.-C. et al.: "Mapping Proton and Carbon Dioxide Electrocatalytic Reductions at a Rh Complex by <i>In Situ</i> Spectroelectrochemical NMR" with the following abstract: <br> <blockquote>Detailed molecular level understanding of organometallic electrocatalytic systems is required to fully exploit their technological potential to store, distribute, and utilise renewable energy in chemical form. However, <i>in situ</i> methods providing high resolution information on the structure and reactivity of transient intermediates remain challenging due to incompatible requirements for standard electrochemical and spectroscopic cell designs. Here, we demonstrate the use of spectroelectrochemical nuclear magnetic resonance (SEC-NMR) to enable <i>operando</i> characterisation of molecular species during organometallic electrocatalysis. The electroreduction of a prototypical molecular rhodium(+I) diphosphine complex was studied under aprotic conditions and in the presence of H<sub>2</sub>O and/or CO<sub>2</sub>. By combining multinuclear SEC-NMR, chemical reductions, modelling and simulations, we determine the involved species, their relative concentrations and the competing interconversions. The bielectronic reduction leading to the highly reactive low-valent rhodium(−I) intermediate and subsequent protonation of that species into a Rh–hydride complex was followed in a time-resolved manner. Deuterium labelling and <i>ex situ</i> NMR analysis after SEC-NMR electrolysis revealed that under aprotic conditions the proton source substantially arises from Hofmann elimination of the <i>n</i>Bu<sub>4</sub>NPF<sub>6</sub> electrolyte in addition to the acetonitrile solvent. The reactivities of the Rh(−I) and the Rh–H complexes were further monitored under turnover conditions, providing direct molecular insights into bifurcating electrocatalytic pathways for hydrogen evolution and CO<sub>2</sub> reduction.</blockquote> Description of folder contents - <b> switch to tree view </b>: <ul> <li><b>UV-Vis_data</b> contains ASCII files that represent data displayed in figure 2. The first row in all ASCII files states the point in time in seconds of the respective measurement. The following columns alternatingly state wavelength in nm and absorbance in arbitrary units (a.u.) of the respective measurements. <ul> <li>CA_at_-2V_blank.dat includes several measurements used as blank.</li> <li>CA_at_-2V_0s+1s+5s+30s.dat represents measurements during chronoamperometry at -2V after 0s, 1s, 5s and 30s.</li> <li>CA_at_-2V_0s+1s+5s+30s_calc_blank.dat represents measurements during chronoamperometry at -2V after 0s, 1s, 5s and 30s considering the blank measurement.</li> </ul> </li> <li><b>NMR_data</b> contains NMR raw data from TopSpin. Subfolders are named according the scheme: X_Y_Z<br> X: Experiment with or without Rh complex: either 'Rh' or 'noRh'.<br> Y: Gaseous environment/electrolyte saturation of experiment: either 'Ar' or '13CO2'.<br> Z: Type of solvent: either 'CD3CN+THF-d8', 'THF-d8', 'THF' or 'CH3CN'. '+H2O' or '+D2O' indicates the addition of 20µL H2O or D2O, respectively.<br> These folders contain subfolders each representing a single measurement. These subfolders are consecutively numbered representing the chronological order of measurements. <ul> <li>Rh_Ar_CD3CN+THF-d8: <sup>31</sup>P spectra displayed in Figure 2 (top left) and evaluated in S5, S6 and S12 are stored in folders '1' to '13' in subfolder '31P'; <sup>1</sup>H spectra displayed in Figure S7 are stored in folders '1' to '13' in subfolder '1H'; the <i>ex situ</i> <sup>1</sup>H spectrum displayed in figure S8 and S10 is stored in folder 'ex_situ' in subfolder '1H'; <sup>2</sup>H spectra displayed in figure S9 are stored in folders '1' and '2' in subfolder '2H'; the <i>ex situ</i> <sup>31</sup>P spectrum displayed in figure S11 is stored in folder 'ex_situ' in subfolder '31P'.</li> <li>Rh_Ar_THF-d8+H2O: <sup>31</sup>P spectra displayed in Figure 2 (bottom left) and evaluated in S13 and S16 are stored in folders '1' to '12' in subfolder '31P'; <sup>1</sup>H spectra displayed in Figure S14 are stored in folders '1' to '13' in subfolder '1H'; the <i>ex situ</i> <sup>1</sup>H spectrum displayed in figure S15 is stored in folder 'ex_situ' in subfolder '1H'.</li> <li>Rh_13CO2_CH3CN: <sup>31</sup>P spectra displayed in Figure 2 (top right) and evaluated in S17 (left) and S18 (left) are stored in folders '1' to '5' in subfolder '31P'; <sup>13</sup>C spectra displayed in Figure S20 are stored in folders '1' to '6' in subfolder '13C'.</li> <li>Rh_13CO2_THF-d8+H2O: <sup>31</sup>P spectra displayed in Figure 2 (bottom right) and evaluated in S17 (right) and S18 (right) are stored in folders '1' to '13' in subfolder '31P'; <sup>13</sup>C spectra displayed in Figure S21 are stored in folders '1' to '6' in subfolder '13C'; <sup>1</sup>H spectra are stored in folders '1' to '13' in subfolder '1H'; the <i>ex situ</i> <sup>1</sup>H spectrum displayed in Figure S19 is stored in folder 'ex_situ' in subfolder '1H'; the <i>ex situ</i> <sup>31</sup>P spectrum is stored in folder 'ex_situ' in subfolder '31P'; the <i>ex situ</i> <sup>13</sup>C spectrum is stored in folder 'ex_situ' in subfolder '13C'.</li> <li>noRh_Ar_THF+H2O: <sup>31</sup>P spectra displayed in Figure S22 and evaluated in Figure S23 are stored in folders '1' to '13' in subfolder '31P'; <sup>1</sup>H spectra are stored in folders '1' to '13' in subfolder '1H'; the <i>ex situ</i> <sup>1</sup>H spectrum displayed in Figure S24 is stored in folder 'ex_situ' in subfolder '1H'; the <i>ex situ</i> <sup>31</sup>P spectrum is stored in folder 'ex_situ' in subfolder '31P'.</li> </ul> </li> <li><b>Electrochemical_data</b> contains raw data from EC-Lab acquired during spectroelectrochemical NMR experiments. The respective subfolders are named according the same scheme as the respective NMR data folder (see above). All .mps files describe the parameters and order of electrochemical experiments, which are stored as binary EC-Lab .mpr files. For all experiments, the order of measurements was: EIS, OCV, CP and a second OCV. <ul> <li>Rh_Ar_CD3CN+THF-d8: 221121_a_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+CD3CN_Ar.mps</li> <li>Rh_Ar_THF-d8+H2O: 221115_d_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+H2O.mps</li> <li>Rh_13CO2_CH3CN: 221010_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_CH3CN+13CO2.mps</li> <li>Rh_13CO2_THF-d8+H2O: 250326_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+13CO2+H2O.mps</li> <li>noRh_Ar_THF+H2O: 221130_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF+H2O.mps</li> </ul> </li> <li><b>Electrolysis_data</b> contains chronoamperometry (CA) electrolysis data and gas chromatography (GC) data acquired during CO<sub>2</sub> and CO<sub>2</sub>/H<sub>2</sub>O electrolysis experiments. The folder is divided into subfolders according to the electrolyte composition. The .txt files are stored in the German (de-DE) format, with commas as decimal digit separator. <ul> <li><b>Electrolysis-CO2</b> contains data from CO<sub>2</sub> electrolysis experiments. Electrolysis A and B are two repeated experiments under equal conditions. <ul> <li><b>Electrolysis A</b>: <ul> <li>A_CA-Electrolysis-CO2.txt contains chronoamperometry data of the electrolysis experiment. Columns are: time in seconds, working electrode potential (Ewe) in V, current in mA, and charge in C.</li> <li><b>GC-Calibration</b> subfolder contains calibration measurements with defined gas mixtures (20%, 40%, 60%, 80%, 100%) used for quantification of GC analysis.</li> <li><b>GC-Electrolysis</b> subfolder contains GC measurements during electrolysis at different time points (0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h) and a blank measurement (0 h). Each file lists peak tables and compound results including retention time, peak area, height, concentration, and identification of gas species (e.g., H<sub>2</sub>, O<sub>2</sub>, N<sub>2</sub>, CO, CO<sub>2</sub>).</li> </ul> </li> <li><b>Electrolysis B</b>: <ul> <li>B_CA-Electrolysis-CO2.txt contains chronoamperometry data of the electrolysis experiment.</li> <li><b>GC-Calibration</b> subfolder contains calibration measurements with defined gas mixtures (38%, 50%, 65%, 86%, 100%).</li> <li><b>GC-Electrolysis</b> subfolder contains GC measurements during electrolysis at different time points (0.5 h to 4 h in 0.5 h intervals) and a blank measurement (0 h).</li> </ul> </li> </ul> </li> <li><b>Electrolysis-CO2-H2O</b> contains data from CO<sub>2</sub> electrolysis experiments with addition of H<sub>2</sub>O. <ul> <li>C_CA-Electrolysis-CO2-H2O.txt contains chronoamperometry data of the electrolysis experiment.</li> <li><b>GC-Calibration</b> subfolder contains calibration measurements with defined gas mixtures (20%, 40%, 60%, 80%, 100%).</li> <li><b>GC-Electrolysis</b> subfolder contains GC measurements during electrolysis at different time points (0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h) and a blank measurement (0 h).</li> </ul> </li> </ul> </li> <li><b>DFT-files</b> contains data from density functional theory (DFT) calculations performed with Gaussian16. The data are organized in three subfolders: <ul> <li><b>out-files-DFT</b> contains Gaussian output files (*.out) for all calculated species. These files include input specifications (basis sets, functional, charge, multiplicity), SCF convergence, optimized geometries, and calculated electronic energies. Example species include CO, CO<sub>2</sub>, H<sub>2</sub>O, HCO<sub>2</sub><sup>–</sup>, H<sub>3</sub>O<sup>+</sup>, and various Rh complexes in different oxidation states and with different ligands (e.g., Rh(0)-CO, Rh(I)-CO<sub>2</sub>H, Rh(-I)).</li> <li><b>xyz-files-optimized</b> contains Cartesian coordinates of the optimized geometries (*.xyz) for the same set of molecules and complexes. Each line lists the atom type followed by its x, y, z coordinates in Å. Example (opt_CO.xyz): <pre> C 0.000000000 0.000000000 -0.640356000 O 0.000000000 0.000000000 0.480267000 </pre></li> <li><b>xyz-files-start</b> contains the starting geometries (*.xyz) used as input for the DFT optimizations, with the same file structure as the optimized xyz files.</li> </ul> </li> </ul>

Kind of Data:

Experimental data

Methodology and Processing

Sources Statement

Data Access

Other Study Description Materials

Other Study-Related Materials

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221010_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_CH3CN+13CO2_01_PEIS_C01.mpr

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application/octet-stream

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221010_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_CH3CN+13CO2_02_OCV_C01.mpr

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application/octet-stream

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221010_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_CH3CN+13CO2_03_CP_C01.mpr

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application/octet-stream

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221010_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_CH3CN+13CO2_04_OCV_C01.mpr

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application/octet-stream

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221010_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_CH3CN+13CO2.mps

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application/octet-stream

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221115_d_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+H2O_01_PEIS_C01.mpr

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application/octet-stream

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221115_d_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+H2O_02_OCV_C01.mpr

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application/octet-stream

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221115_d_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+H2O_03_CP_C01.mpr

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application/octet-stream

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221115_d_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+H2O_04_OCV_C01.mpr

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application/octet-stream

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221115_d_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+H2O.mps

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application/octet-stream

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221121_a_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+CD3CN_Ar_01_PEIS_C01.mpr

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application/octet-stream

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221121_a_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+CD3CN_Ar_02_OCV_C01.mpr

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application/octet-stream

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221121_a_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+CD3CN_Ar_03_CP_C01.mpr

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application/octet-stream

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221121_a_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+CD3CN_Ar_04_OCV_C01.mpr

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application/octet-stream

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221121_a_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+CD3CN_Ar.mps

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application/octet-stream

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221130_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF+H2O_01_PEIS_C01.mpr

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application/octet-stream

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221130_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF+H2O_02_OCV_C01.mpr

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application/octet-stream

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221130_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF+H2O_03_CP_C01.mpr

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application/octet-stream

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221130_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF+H2O_04_OCV_C01.mpr

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application/octet-stream

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221130_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF+H2O.mps

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application/octet-stream

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250326_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+13CO2+H2O_01_PEIS_C01.mpr

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application/octet-stream

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Label:

250326_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+13CO2+H2O_02_OCV_C01.mpr

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application/octet-stream

Other Study-Related Materials

Label:

250326_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+13CO2+H2O_03_CP_C01.mpr

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application/octet-stream

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Label:

250326_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+13CO2+H2O_04_OCV_C01.mpr

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application/octet-stream

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250326_b_inOp_RhCell_GC-WE_Ptmesh-CE_Pt-RE_Rh_THF-d8+13CO2+H2O.mps

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application/octet-stream

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A_100% Testing Gas.txt

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text/plain

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A_20% Testing Gas.txt

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A_40% Testing Gas.txt

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A_60% Testing Gas.txt

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A_80% Testing Gas.txt

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A_After 0,5h.txt

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A_After 1,5h.txt

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A_After 1h.txt

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A_After 2,5h.txt

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A_After 2h.txt

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A_After 3h.txt

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text/plain

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A_Blank 0h.txt

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text/plain

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A_CA-Electrolysis-CO2.txt

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text/plain

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B_100% Testing Gas.txt

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text/plain

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B_38% Testing Gas.txt

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B_50% Testing Gas.txt

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B_65 % Testing Gas.txt

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B_86% Testing Gas.txt

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B_After 0,5h.txt

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B_After 1,0h.txt

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B_After 1,5h.txt

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B_After 2,0h.txt

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B_After 2,5h.txt

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B_After 3,0h.txt

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B_After 3,5h.txt

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B_After 4,0h.txt

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B_Blank 0h.txt

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B_CA-Electrolysis-CO2.txt

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text/plain

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CA_at_-2V_0s+1s+5s+30s_calc_blank.dat

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text/x-fixed-field

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CA_at_-2V_0s+1s+5s+30s.dat

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text/x-fixed-field

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CA_at_-2V_blank.dat

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text/x-fixed-field

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C_After 0,5h.txt

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text/plain

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C_After 1,5h.txt

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C_After 1h.txt

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C_After 2,5h.txt

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C_After 2h.txt

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C_After 3,5h.txt

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C_After 3h.txt

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C_After 4h.txt

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C_Blank 0h.txt

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C_CA-Electrolysis-CO2-H2O.txt

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text/plain

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CO2.out

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application/octet-stream

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CO.out

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application/octet-stream

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H2O.out

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application/octet-stream

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H3O+.out

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application/octet-stream

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HCO2-.out

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application/octet-stream

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noRh_Ar_THF+H2O.7z

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application/x-7z-compressed

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opt_CO2.xyz

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chemical/x-xyz

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opt_CO.xyz

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chemical/x-xyz

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opt_H2O.xyz

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chemical/x-xyz

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opt_H3O+.xyz

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chemical/x-xyz

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opt_HCO2-.xyz

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chemical/x-xyz

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opt_Rh(0)-CO2H-.xyz

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chemical/x-xyz

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opt_Rh(0)-CO.xyz

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chemical/x-xyz

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opt_Rh(0)-H-.xyz

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chemical/x-xyz

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opt_Rh(I)-CO2H.xyz

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chemical/x-xyz

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opt_Rh(I)-CO2-.xyz

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chemical/x-xyz

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opt_Rh(I)-CO+.xyz

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chemical/x-xyz

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opt_Rh(I)-H.xyz

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chemical/x-xyz

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opt_Rh(I)-OCOH.xyz

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chemical/x-xyz

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opt_Rh(-I).xyz

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chemical/x-xyz

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opt_Rh(I).xyz

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chemical/x-xyz

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README.html

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text/html

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Rh(0)-CO2H-.out

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application/octet-stream

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Rh(0)-CO.out

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application/octet-stream

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Rh(0)-H-.out

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application/octet-stream

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Rh_13CO2_CH3CN.7z

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application/x-7z-compressed

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Rh_13CO2_THF-d8+H2O.7z

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application/x-7z-compressed

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Rh_Ar_CD3CN+THF-d8.7z

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application/x-7z-compressed

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Rh_Ar_THF-d8+H2O.7z

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application/x-7z-compressed

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Rh(I)-CO2H.out

Notes:

application/octet-stream

Other Study-Related Materials

Label:

Rh(I)-CO2-.out

Notes:

application/octet-stream

Other Study-Related Materials

Label:

Rh(I)-CO+.out

Notes:

application/octet-stream

Other Study-Related Materials

Label:

Rh(I)-H.out

Notes:

application/octet-stream

Other Study-Related Materials

Label:

Rh(I)-OCOH.out

Notes:

application/octet-stream

Other Study-Related Materials

Label:

Rh(-I).out

Notes:

application/octet-stream

Other Study-Related Materials

Label:

Rh(I).out

Notes:

application/octet-stream

Other Study-Related Materials

Label:

start_CO2.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_CO.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_H2O.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_H3O+.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_HCO2-.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_Rh(0)-CO2H-.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_Rh(0)-CO.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_Rh(0)-H-.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_Rh(I)-CO2H.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_Rh(I)-CO2-.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_Rh(I)-CO+.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_Rh(I)-H.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_Rh(I)-OCOH.xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_Rh(-I).xyz

Notes:

chemical/x-xyz

Other Study-Related Materials

Label:

start_Rh(I).xyz

Notes:

chemical/x-xyz