DOI: 10.5281/zenodo.8203041
title: Photophysical and Spectroscopic dataset for Ag–In–Zn–S Quaternary Nanocrystals Prepared from InCl2 Precursor as Visible Light Photocatalysts of Aromatic Aldehyde Photoreduction

description: (1) Energy-dispersive spectra of alloyed Ag-In-Zn-S nanocrystals before (Ag1.0In1.5Zn0.3S3.3(S3.0) (R)  and  Ag1.0In10.3Zn12.4S11.8(S28.3) (G)) and after the exchange of initial capping ligands for 11-mercaptoundecanoic acid (Ag1.0In1.3Zn0.5S3.3(S3.0) (R-MUA) and (Ag1.0In2.7Zn30.0S90.0(S34.5) (G-MUA)).

(2) HR-TEM images of Ag1.0In1.5Zn0.3S3.3(S3.0) (R)  and  Ag1.0In10.3Zn12.4S11.8(S28.3) (G) alloyed nanocrystals.

(3) UV-vis-NIR spectra of toluene dispersion of Ag1.0In1.5Zn0.3S3.3(S3.0) (R),  Ag1.0In10.3Zn12.4S11.8(S28.3) (G) and water dispersion of Ag1.0In1.3Zn0.5S3.3(S3.0) (R-MUA), Ag1.0In2.7Zn30.0S90.0(S34.5) (G-MUA) nanocrystals.

(4) Photoluminescence excitation and emission spectra of toluene dispersion of Ag1.0In1.5Zn0.3S3.3(S3.0) (R),  Ag1.0In10.3Zn12.4S11.8(S28.3) (G) nanocrystals and the corresponding spectra of water dispersion of Ag1.0In1.3Zn0.5S3.3(S3.0) (R-MUA), Ag1.0In2.7Zn30.0S90.0(S34.5) (G-MUA) nanocrystals.

(5) Photoluminescence decay curves of toluene dispersion of Ag1.0In1.5Zn0.3S3.3(S3.0) (R),  Ag1.0In10.3Zn12.4S11.8(S28.3) (G) and water dispersion of Ag1.0In1.3Zn0.5S3.3(S3.0) (R-MUA), Ag1.0In2.7Zn30.0S90.0(S34.5) (G-MUA) nanocrystals.

(6) XPS survey and high-resolution spectra of alloyed Ag-In-Zn-S nanocrystals before Ag1.0In1.5Zn0.3S3.3(S3.0) (R) and  Ag1.0In10.3Zn12.4S11.8(S28.3) (G)  and after the exchange of initial capping ligands for 11-mercaptoundecanoic acid (Ag1.0In1.3Zn0.5S3.3(S3.0) (R-MUA) and Ag1.0In2.7Zn30.0S90.0(S34.5) (G-MUA)).

(7) 1H, 1H-1H COSY and 13C, 1H-13C HMQC NMR spectra of the photocatalytic reduction reaction mixture used for the photocatalytic reduction of 4-chlorobenzaldehyde and furfural.

(8) GC chromatogram of the photocatalytic reduction reaction mixture used for photocatalytic reduction of 4-chlorobenzaldehyde.

(9) DMPO spin-trapping EPR spectra of  toluene dispersion of Ag1.0In1.5Zn0.3S3.3(S3.0) (R),  Ag1.0In10.3Zn12.4S11.8(S28.3) (G) nanocrystals and reaction mixture used for the photocatalytic reduction of furfural.

 

This work was supported by the National Science Centre of Poland, Grant No. 2022/45/B/ST5/02120.
description: (1) Elemental analysis of alloyed Ag-In-Zn-S nanocrystals was carried out with a multichannel Quantax 400 energy-dispersive X-ray spectroscopy (EDS) system with a 125 eV xFlash detector 5010 (Bruker) using a 15 kV electron beam energy.

(2) High-resolution images were acquired by a Tecnai TF20 X-TWIN (Thermo Fisher Scientific) microscope operated at 200 kV.

(3) UV-vis-NIR spectra were registered using a Cary 5000 (Varian) spectrometer.

(4) Steady-state PL spectra of toluene solutions of samples were measured with FLS-980 fluorescence spectrophotometer equipped with a 450 W Xe lamp and photomultiplier (Hamamatsu, R928P) detector with a standard 10 mm cuvette (λexc = 375 nm).

(5) The PL lifetime measurement was performed with a time correlated single photon counting (TCSPC) method on FLS-980 fluorescence spectrophotometer. The excitation wavelength (405 nm) was obtained using the picosecond pulsed diode laser (EPL - 405 nm, Edinburgh Instruments).

(6) Survey and high-resolution (HR) XPS spectra were recorded using a PHI 5000 VersaProbeTM spectrometer (ULVAC-PHI, Chigasaki, Japan) with monochromatic Al Ka radiation (hn = 1486.6 eV). The HR XPS spectra were collected with the hemispherical analyzer at the pass energy of 23.5 eV, the energy step size of 0.1 eV and the photoelectron take off angle of 45° with respect to the surface plane. The CasaXPS software was used to evaluate the obtained XPS data. Deconvolution of HR XPS spectra were performed using a Shirley background and a Gaussian peak shape with 30% Lorentzian character. The binding energy (Eb) scale of all detected spectra was referenced by setting the BE of C1s to 284.8eV. For quantification the PHI Multipak sensitivity factors and determined transmission function of the spectrometer were used.

(7) 1H, 1H-1H COSY and 13C NMR spectra were recorded on a Bruker Avance (400 MHz) spectrometer and referenced with respect to tetramethylsilane (TMS) and solvents.

(8) GC-MS analyses were performed using the system equipped with a gas chromatograph GC 7890A coupled with a mass detector VL MSD 5975C, both from Agilent. A capillary column HP-1701 30m´250mm´0.25mm was used, with helium as a carrier at 1 mL/min. Sample volume was 0.1 ml at split value of 1:50 and the injector temperature 200 °C. The temperature program was as follows: from an initial temperature of 40 °C held for 2 min a linear temperature increase of 25 °C/min to 250 °C was applied. After reaching 250 °C the temperature was held constant for 25 min. No additional peaks were recorded when the temperature range was extended to 300 °C using the same temperature program. The analyses were performed using ES ionization, chromatograms were acquired in the TIC mode at m/z 10-700. P.a. grade chloroform was used for preparing the solutions of concentration of 30 mg/mL.

(9) Electron paramagnetic resonance (EPR) spectra were obtained with a Bruker EMX EPR spectrometer (Bruker-Biospin, Germany) operating at the X-band frequency (9.7 GHz) at room temperature. Typical instrument parameters were as follows: central field, 3480 G; modulation amplitude, 1.0 G; gain, 4.48×104 G; microwave power, 31.81 mW; sweep width, 100 G.