Supplementary Materials Solvothermal Crystallization of Ag/AgxO-AgCl Composites: Effect of Different Chloride Sources/Shape-Tailoring Agents

Zsejke-Réka Tóth 1,2, Saurav Kumar Maity 3, Tamás Gyulavári 1, Enikő Bárdos 1, Lucian Baia 2,4, Gábor Kovács 1,2, Seema Garg 3, Zsolt Pap 1,2,5,* and Klara Hernadi 1,6,*

1 Faculty of Science and Informatics, Department of Applied and Environmental Chemistry, University of Szeged, Rerrich Béla sqr. 1, HU-6720 Szeged, Hungary; [email protected] (Z.-R.T.); [email protected] (T.G.); [email protected] (E.B.); [email protected] (G.K.) 2 Nanostructured Materials and Bio-Nano-Interfaces Center, Interdisciplinary Research Institute on Bio- Nano-Sciences, Babeș-Bolyai University, Treboniu Laurian str. 42, RO-400271 Cluj-Napoca, Romania; [email protected] 3 Department of Chemistry, Amity Institute of Applied Sciences, Amity University, Sector-125, Noida 201313, Uttar Pradesh, India; [email protected] (S.K.M.); [email protected] (S.G.) 4 Faculty of Physics, Babeș-Bolyai University, M. Kogălniceanu str. 1, RO-400084 Cluj-Napoca, Romania 5 Institute of Research-Development-Innovation in Applied Natural Sciences, Babes-Bolyai University, Fântânele str. 30, RO-400294 Cluj-Napoca, Romania 6 Institute of Physical Metallurgy, Metal Forming and Nanotechnology; University of Miskolc; Miskolc- Egyetemváros, HU-3515 Miskolc, Hungary * Correspondence: [email protected] (Z.P.); [email protected] (K.H.)

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Copyright: © 2021 by the authors. Submitted for possible open access publication under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). Catalysts 2021, 11, 379. https://doi.org/10.3390/catal11030379 2 of 5

0.50

0.80 HCl NaCl KCl

220/200 111/200 0.45 0.75

0.70 0.40

(220)/(200)

0.65 (111)/(200) 0.35

Intensity Intensity

0.60 Intensity

0.30 0.55

N PVP SDS N PVP SDS N PVP SDS 0.50 0.25 Sample

Figure S1. Structural properties of AgCl: Intensity ratios of (111)/(200) (red line) and (220)/(200) (black line) crystallographic planes.

Silver based material 1 μm

Figure S2. Appearance of small particles on the surface of the catalyst: SEM micrograph of AgCl_NaCl_SDS.

NØ PVP SDS

Na+

500 nm 500 nm 500 nm

K+

500 nm 500 nm 500 nm Figure S3. In-depth analysis of the AgCl microcrystal’s morphology: transmission electron micros- copy (TEM micrographs of AgCl photocatalysts prepared using different shape-tailoring agents (NØ ; PVP and SDS), alkali metals (Na+, K+), and H+.

Catalysts 2021, 11, 379. https://doi.org/10.3390/catal11030379 3 of 5

35 a

30

25

20 AgCl_HCl_N Reflectance (%) AgCl_HCl_PVP AgCl_HCl_SDS 15 AgCl_NaCl_N AgCl_NaCl_PVP AgCl_NaCl_SDS AgCl_KCl_N 10 AgCl_KCl_PVP AgCl_KCl_SDS

300 400 500 600 700 800  (nm) HCl NaCl KCl AgCl_HCl_N b AgCl_NaCl_N c AgCl_KCl_N d AgCl_HCl_PVP AgCl_NaCl_PVP AgCl_KCl_PVP AgCl_HCl_SDS AgCl_NaCl_SDS AgCl_KCl_SDS

)

)

)

a.u.

(

a.u.

a.u.

(

(







dR/d

dR/d

dR/d

330 345 360 375 390 405 420 330 345 360 375 390 405 420 330 345 360 375 390 405 420  (nm)  (nm)  (nm) Figure S4. Optical parameters investigation of AgCl photocatalyst: (a) diffuse reflectance spectra (DRS) spectra using different shape-tailoring agents (NØ ; PVP and SDS), alkali metals (Na+, K+), and H+ and the first-order derivative of DRS spectra: (b) AgCl_HCl; (c) AgCl_NaCl; and (d) AgCl_KCl sample series.

50 50 AgCl_HCl_0.1PVP AgCl_HCl_0.2PVP 45 đ=0.92 μm 45 đ=1.11 μm 40 a 40 b 35 35 30 30

25 25 20 20 15 15

Particle size distribution (%) Particle 10 size distribution (%) Particle 10 5 5 0 0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 Diameter (m) Diameter (m) 50 50 AgCl_HCl_0.6PVP AgCl_HCl_1.0PVP 45 đ=1.04 μm 45 đ=1.05 μm ) 40 c 40 d

%

( 35 35 30 30

25 25 20 20 15 15

Particle size distribution Particle 10 size distribution (%) Particle 10 5 5 0 0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 Diameter (m) Diameter (m) Figure S5. Particle size distribution of the samples: (a) AgCl_HCl_0.1PVP; (b) AgCl_HCl_0.2PVP; (c) AgCl_HCl_0.6PVP; and (d) AgCl_HCl_1.0PVP.

Catalysts 2021, 11, 379. https://doi.org/10.3390/catal11030379 4 of 5

45 AgCl_HCl_0.1PVP AgCl_HCl_0.2PVP a 40 AgCl_HCl_0.6PVP AgCl_HCl_1.0PVP 35

30

25

20 b

Reflectance (%)

15 )

a.u.

(

dR/dλ (a.u.)



10 dR/d

5 340 360 380 400 420  (nm) 0 300 400 500 600 700 800  (nm)

Figure S6. The effect of PVP amount on the optical properties of the catalysts: (a) DRS spectra; (b) inset graph: first-order derivative DRS spectra of the AgCl_HCl_xPVP samples series (x = 0.1, 0.2, 0.6, and 1.0 g).

Table S1. Summary of the diffractions patterns, band gap energy value of the samples and conversion values of the degradation of MO.

Summary of the diffraction’s patterns of the samples Materials with a high Possibly covered Conversion of Materials with a low percentage Band gap Sample percentage diffraction signals degradation of energy (eV) AgCl AgCl AgCl 1st 2nd 3rd AgClO4 AgClO3 Ag AgClO3 a MO(%)

(≈27.7°) (≈32.2°) (≈46.2°) (≈27.6°) (≈32.6°) (≈45.9°) (≈25.0°) (≈29.0°) (≈38.0°) (≈41.4°) AgCl_HCl_NØ x x x x x x x x 2.34 0.00 AgCl_HCl_PVP x x x x x x 2.41 21.7 AgCl_HCl_SDS x x x x x x x x x 2.67 16.4 AgCl_NaCl_NØ x x x x x 2.55 5.6 AgCl_NaCl_PVP x x x x x x 2.38 9.3 AgCl_NaCl_SDS x x x x x x 2.35 5.8

Cation effect AgCl_KCl_NØ x x x x x x x x x 2.49 9.8 AgCl_KCl_PVP x x x x x x x 2.49 11.8 AgCl_KCl_SDS x x x x x x x 2.49 9.9 AgCl_HCl_0.1PVP x x x x x x x x x 2.17 23.7

AgCl_HCl_0.2PVP x x x x x x x x 2.24 24.2

PVP

effect AgCl_HCl_0.6PVP x x x x x x 2.33 32.8

amount AgCl_HCl_1.0PVP x x x x x x x x 2.63 27.6 00-031- 00-101- 00-001- 00-101- COD card no. 00-031-1238 1239 0506 1167 0506 a not all reflections are visible in XRD patterns