Role of Pd in the Electrochemical Hydrogenation of Nitrobenzene Using CuPd Electrodes

# Dataset of "Role of Pd in the Electrochemical Hydrogenation of Nitrobenzene Using CuPd Electrodes"

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## GENERAL INFORMATION----------------------

1. Dataset title: "Role of Pd in the Electrochemical Hydrogenation of Nitrobenzene Using CuPd Electrodes"

2. Authorship:      Name: David Carvajal    Institution: Institute of Advanced Materials (INAM), Universitat Jaume I, 12006 Castelló, Spain    ORCID: 0000-0003-3723-0371

    Name: Ramón Arcas    Institution: Institute of Advanced Materials (INAM), Universitat Jaume I, 12006 Castelló, Spain    ORCID: 0000-0001-5813-2768

    Name: Camilo A. Mesa    Institution: Institute of Advanced Materials (INAM), Universitat Jaume I, 12006 Castelló, Spain    ORCID: 0000-0002-8450-2563

    Name: Sixto Giménez    Institution: Institute of Advanced Materials (INAM), Universitat Jaume I, 12006 Castelló, Spain    ORCID: 0000-0002-4522-3174        Name: Francisco Fabregat-Santiago    Institution: Institute of Advanced Materials (INAM), Universitat Jaume I, 12006 Castelló, Spain    Email:     ORCID: 0000-0002-7503-1245

    Name: Elena Mas-Marzá    Institution: Institute of Advanced Materials (INAM), Universitat Jaume I, 12006 Castelló, Spain    Email:      ORCID: 0000-0002-2308-0635

## FILE DESCRIPTION--------------### Figure 2- Fig2.txt : Cyclic voltammetries for the reduction of nitrobenzene (30 × 10−3 m), using Cu or CuPd as working electrode, Pt as counter electrode and Ag/AgCl as reference, in a mixture of water/acetonitrile 70/30% (V/V), with 0.25 m of Na2HPO4 as electrolyte at 10 mV s−1 scan rate.

### Figure 3- Fig3a.txt : (%) Conversion of nitrobenzene and (%) yield of species in the electrolysis as a function of time for initial concentrations of nitrobenzene of 15 × 10−3 M, for Cu electrodes in 0.25 m NaH2PO4 at −0.8 V (vs Ag/AgCl) in 70/30 water/acetonitrile solution.- Fig2b.txt : (%) Conversion of nitrobenzene and (%) yield of species in the electrolysis as a function of time for initial concentrations of nitrobenzene of 30 × 10−3 m, for Cu electrodes in 0.25 m NaH2PO4 at −0.8 V (vs Ag/AgCl) in 70/30 water/acetonitrile solution.

### Figure 4- Fig4a.txt : (%) Conversion of nitrobenzene and (%) yield of species in the electrolysis as a function of time for initial concentrations of nitrobenzene of 15 × 10−3 M, for CuPd electrodes in 0.25 m NaH2PO4 at −0.8 V (vs Ag/AgCl) in 70/30 water/acetonitrile solution.- Fig4b.txt : (%) Conversion of nitrobenzene and (%) yield of species in the electrolysis as a function of time for initial concentrations of nitrobenzene of 30 × 10−3 M, for CuPd electrodes in 0.25 m NaH2PO4 at −0.8 V (vs Ag/AgCl) in 70/30 water/acetonitrile solution.

### Figure 5- Fig5a.txt : first-order kinetic constant for nitrobenzene reduction 15 × 10−3 and 30 × 10−3 M of nitrobenzene initial concentration.- Fig5b.txt : aniline rate formation for Cu and CuPd electrodes with 15 × 10−3 and 30 × 10−3 M of nitrobenzene initial concentration.

### Figure 8- Fig8a.txt : J–V curves for the fitting of IS measurements with the corresponding equivalent circuit as a function of VF, the potential after correcting the voltage drop at the series resistance.- Fig8b.txt : Cdl for the fitting of IS measurements with the corresponding equivalent circuit as a function of VF, the potential after correcting the voltage drop at the series resistance.- Fig8c.txt : Css for the fitting of IS measurements with the corresponding equivalent circuit as a function of VF, the potential after correcting the voltage drop at the series resistance.- Fig8d.txt : R ct for the fitting of IS measurements with the corresponding equivalent circuit as a function of VF, thepotential after correcting the voltage drop at the series resistance.

### Figure S6-FigS6.txt : Stability of the CuPd electrode with six cycles of reduction of 30 mM of nitrobenzene.

### Figure S7-FigS7.txt : Cyclic voltammetries for the reduction of nitrobenzene (30 mM), nitrosobenzene (30 mM), phenylhydroxylamine (30mM) and HER (only electrolyte), using A) Cu or B) CuPd as working electrode, Pt as counter electrode and Ag/AgCl as reference, in a mixture of water/acetonitrile 70/30 % (V/V) with 0.25 M of NaH2PO4 as electrolyte at 10 mV/s scan rate. C) Comparison of nitrosobenzene and phenylhydroxylamine data for the two electrodes.

### Figure S8-FigS8.txt : Elution time for nitrobenzene, aniline, intermediaries and side-products. Δ:phenylhydroxylamine, Δ:aniline, Δ: nitrobenzene, Δ: nitrosobenzene, Δ: azoxybenzene, Δ: azobenzene 

### Figure S9-FigS9.txt : Calibrations curves were obtained from the area of the HPLC peaks. A) nitrobenzene (270 nm), B) aniline (230 mm), C) nitrosobenzene (310nm), D) phenylhydroxylamine (230nm), E) azoxybenzene (330 nm), F) azobenzene (330 nm).

### Figure S10-FigS10.txt : HPLC chromatograms at different reaction times for 30 mM nitrobenzene reduction experiment with CuPd electrode at 230 nm. Time elution 3.4: aniline, 9.6:nitrobenzene.

### Figure S11-FigS11a.txt : The fit of experimental data for electrolysis to initial concentration of 15 mM and 30 mM of nitrobenzene in 0.25 of NaH2PO4 at -0.8 vs Ag/AgCl (V) in 70/30 water/acetonitrile solution. First-order kinetics for nitrobenzene reduction.-FigS11c.txt : The fit of experimental data for electrolysis to initial concentration of 15 mM and 30 mM of nitrobenzene in 0.25 of NaH2PO4 at -0.8 vs Ag/AgCl (V) in 70/30 water/acetonitrile solution. Formation rate of aniline at thebeginning of the reaction C = vt equation.

### Figure S12-FigS12.txt : Faraday efficiency to aniline as a function of time for 15 mM and 30 mM of initial concentration of nitrobenzene with Cu and CuPd electrodes.

### Figure S13-FigS13a.txt : Css values as a function of Vf from the EIS fitting of the equivalent circuit shown in Figure 7.-FigS13b.txt : Rss values as a function of Vf from the EIS fitting of the equivalent circuit shown in Figure 7.

### Figure S14-FigS14a.txt : J-V curves as a function of potential. For Cu and CuPd electrodes in acetonitrile with 0.1 M TBAClO4, Cu film as the counter electrode, and Ag/AgNO3 (10 mM) in acetonitrile (0.1 M TBAClO4) as reference electrode. For CuPd electrode in water/acetonitrile with 0.25 M NaH2PO4, Pt wire as the counter electrode, and Ag/AgCl (3 M) like reference electrode. The potential axis for both graphics are in aqueous Ag/AgCl (3M) reference system.-FigS14b.txt : Cdl curves as a function of potential. For Cu and CuPd electrodes in acetonitrile with 0.1 M TBAClO4, Cu film as the counter electrode, and Ag/AgNO3 (10 mM) in acetonitrile (0.1 M TBAClO4) as reference electrode. For CuPd electrode in water/acetonitrile with 0.25 M NaH2PO4, Pt wire as the counter electrode, and Ag/AgCl (3 M) like reference electrode. The potential axis for both graphics are in aqueous Ag/AgCl (3M) reference system.

### Figure S16-FigS16.txt : J-V curves of FTO and Pd decorated FTO (Pd/FTO) in a mixture of water/acetonitrile 70/30 % (V/V) with 0.25M of Na2HPO at 0mM and 30 mM concentrations of nitrosobenzene.

### Figure S17-FigS17b.txt : J-V curves for the samples in Figure 8 compared with control Pd/FTO sample. VF is the potential after correcting the voltage drop at the series resistance.-FigS17c.txt : Cdl (obtained from the fitting of IS measurements. VF is the potential after correcting the voltage drop at the series resistance) for the samples in Figure 8 compared with control Pd/FTO sample.-FigS17d.txt : Rct (obtained from the fitting of IS measurements. VF is the potential after correcting the voltage drop at the series resistance) for the samples in Figure 8 compared with control Pd/FTO sample.